Blocked isocyanate polymer (iv)

ABSTRACT

&#34;BLOCKED&#34; POLYISOCYANATO-CONTAINING POLYMERS WHICH MAY BE OBTAINED VIA THE VINYL POLYMERIZATION OF UNSATURATED DIESTER DIISOCYANATES AS EXEMPLIFIED BY BIS(2-ISOCYANATOETHYL) FUMARATE WITH/WITHOUT ETHYLENICALLY UNSATURATED COMPOUNDS, E.G., STYRENE, VINYL ACETATE, ETC., FOLLOWED BY REACTING THE POLYISOCYANATO GROUPS OF THE RESULTING POLYMERS WITH A MONOFUNCTIONAL ACTIVE HYDROGEN COMPOUND. THE ABOVE REACTIONS MAY ALSO BE REVERSED TO THUS OBTAIN THE &#34;BLOCKED&#34; POLYMERS.

March 2, 1971 BRQTHERTON ETAL 3,567,695

BLOCKED ISOCYANATE POLYMER (IV) Filed April 2, 1968 STRESS-STRAIN CURVE900 r 2 f A b Loadmg V 600- l m v I b m La.) a: ym LW'I'JN'I'HHS THOMASK.BROTHERTON JOHN W.LYNN

By MWUUL/ A T TORNE Y United States Patent 5,567,695 BLOCKED ISOCYANATEPOLYMER (IV) Thomas K. Brotherton and John W. Lynn, Charleston,

W. Va., assignors to Union Carbide Corporation Application Nov. 9, 1964,Ser. No. 409,921, which is a continuation-in-part of application Ser.No. 212,480,

July 25, 1962. Divided and this application Apr. 2,

1968, Ser. No. 718,094

Int. Cl. C08g 22/18 U.S. Cl. 260-775 8 Claims ABSTRACT OF THE DISCLOSUREThis application is a division of application Ser. No. 409,921, now U.S.3,427,346 entitled Novel Olefinically Unsaturated Diisocyanates andProducts Therefrom by T. K. Brotherton and J. W. Lynn, filed Nov. 9,1964 which, in turn, is a continuation-impart of application Ser. No.212,480 abandoned entitled Novel Olefinically Unsaturated Diisocyanatesand Process for Preparation, by T. K. Brotherton and .T. W. Lynn, filedJuly 25, 1962, all of the aforesaid applications being assigned to thesame assignee as the instant application.

This invention relates to novel diisocyanate compositions and toprocesses for preparing the same. In one aspect, the invention relatesto novel polymers of the above-said diisocyanate compositions whichpolymers contain a plurality of ethylenic bonds, i.e., C=C In otheraspect, the invention relates to novel polymers of the above-saiddiisocyanate compositions, said polymers containing a plurality ofpendant isocyanatogroups, i.e., NCO. In a further aspect, the inventionrelates to novel compositions which result from the reaction of novelpolyisocyanates with active hydrogen compounds. In various otheraspects, the invention relates to the preparation of novel cast resinsthermoplastic resins, millable gum stocks and the cured productstherefrom, prepolymers, elastomers, elastic and relatively non-elasticfibers, urethane foams, adhesives, coatings, and the like.

The novel ester diisocyanate compounds which are contemplated can berepresented by Formula I infra:

wherein R represents a member selected from the group consisting ofdivalent, substituted and unsubstituted aliphatic, alicyclic, andaromatic groups, and wherein R represents a divalent olefinicallyunsaturated aliphatic group; with the provisos that (1) when both Rvariables are alkylene groups, e.g., ethylene, R is not a cis-vinylenegroup, i.e.,

and (2) each isocyanato moiety, individually is at least two carbonatoms removed from the 3,567,695 Patented Mar. 2, 1971 moiety of theabove formula. Preferred compounds are those wherein R represents adivalent hydrocarbon group containing from 2 to 12 carbon atoms and Rrepresents a divalent olefinically unsaturated hydrocarbon groupcontaining from 2 to 24 carbon atoms. Particularly preferred compoundsrepresented by Formula I are those wherein R represents a memberselected from the group consisting of alkylene, alkenylene, alkynylene,arylene, arylenealkylene, alkylenearylene, alkarylene,arylenealkenylene, alkenylenearylene, arylenealkynylene,alkynylenearylene, cycloalkylene, cycloalkenylene, alkylcycloalkylene,alkylcycloalkenylene, cycloalkylenealkylene and cycloalkenylalkylenegroups containing from 2 to 12 carbon atoms; and R represents analkenylene group containing from 2 to 18 carbon atoms and morepreferably from 2 to 10 carbon atoms.

Illustrative novel diisocyanate compounds encompassed within Formula Isupra include, among others, bis(Z-isocyanatoethyl) fumarate,bis(2-isocyanato-2-methylethyl) fumarate,bis(2-isocyanato-l-methylethyl) fumarate, bis (9-isocyanatononyl)fumarate, bis(1'2-isocyanatododecyl) glutaconate,bis(2-isocyanato-n-propyl) fumarate, bis(4- isocyanatophenyl) alphahydromuconate, bis(2-isocyanatonaphthyl) itaconate,bis(4-isocyanatophenyl) fumarate, bis(3-isocyanatocyclohexyl)glutaconate, bis(4-isocyanato-Z-butenyl) fumarate, and the like.

The term substituted as used throughout the specification and appendedclaims is meant to further define the novel diisocyanates, thederivatives thereof, and the polymeric products thereof, to includethose wherein the aforementioned R groups (of Formula I) can bealiphatic with alicyclic or aromatic substituents; alicyclic withaliphatic or aromatic substituents; or aromatic with aliphatic oralicyclic substituents in addition to other groups hereinafterindicated.

Broadly, the generic inventions are directed to novel diisocyanates (ofFormula I supra) and to novel processes for preparing the same. Withinthe limits of the aforesaid generic inventions there are includedseveral highly desirable embodiments which are described hereinafter indetail.

In one embodiment, highly useful and attractive subclasses of novelester diisocyanates which fall within the metes and bounds of Formula 1supra are those wherein each R represents a substituted or unsubstituteddivalent aliphatic group and R represents a divalent olefinicallyunsaturated aliphatic group containing from 2 to 24 carbon atoms.Preferred compounds within this embodiment are those represented byFormula II infra:

wherein R represents a divalent substituted or unsubstituted aliphaticgroup containing from 2 to 12 carbon atoms and R represents analkenylene group containing from 2 to 24 carbon atoms. Particularlypreferred compounds within this embodiment are those wherein R is amember selected from the group consisting of alkylene, alkenylene,alkynylene, cycloalkylalkylene, cycloalkenylalkylene, and arylalkylenegroups containing from 2 to 10 carbon atoms and R has the same value aspreviously indicated. The divalent R groups can be either straight orbranched chain and need not be the same throughout the molecule.

Illustrative of the novel diisocyanates which fall with in thisembodiment include bis(2-isocyanatoethyl) fumarate,bis(3-isocyanatopropyl) glutaconate, bis(4-isocyanatobutyl) alphahydromuconate, bis(S-isocyanatopentyl) beta-hydromuconate,bis(7-isocyanatoheptyl) itaconate, bis(2,2-dimethyl-3isocyanatopropyl)fumarate, bis(3ethyl-S-isocyanatopentyl) glutaconate,bis(3,4-diethyl-S-isocyanatopentyl) alpha-hydromuconate, bis(4,4

dimethyl-6-isocyanatohexyl) beta-hydromuconate, bis(2-methyl-4-ethyl-6-isocyanatohexyl) itaconate, bis(9-is0- cyanatononyl)fumarate, bis(5,6,7-triethyl-9-isocyanatononyl) fumarate,2-isocyanatoethy1 3-isocyanatopropyl glutaconate, 4-isocyanatobutyl6-isocyanatohexyl alphahydromuconate, 3-isocyanatopropyl8-isocyanatooctyl beta-hydromuconate, S-isocyanatopentyl6-isocyanatohexyl itaconate, 2-methyl-3-isocyanatopropyl2-isocyanatoethyl fumarate, 4-ethyl-7-isocyanatoheptyl 6-isocyanatohexylfumarate, bis(4-isocyanato 2 butenyl) glutaconate,bis(4-isocyanato-2-butenyl) itaconate, bis(2- isocyanatoethyl)citraconate, bis(7-isocyanato-4-heptenyl) fumarate,bis(8-isocyanato-4-octenyl) glutaconate, bis(9-isocyanato-5-nonenyl)itaconate, bis(lO-isocyanato- 6-decenyl) fumarate, bis(3ethyl-S-isocyanato-3-pentenyl) fumarate,bis(3,4-dimethyl-5-isocyanato-3-pen tenyl) glutaconate,bis(2-methyl-4-ethyl-6-isocyanato-2- hexenyl) itaconate, bis(5,6,7triethyl-9-isocyanato-4- nonenyl) glutaconate, 4-isocyanato-2-butenyl3-isocyanatopropyl fumarate, 4-isocyanato2-buteny1 S-isocyanato-3-pentenyl glutaconate, 4-ethyl-7-isocyanato-5-heptenyl6-isocyanato-3-hexenyl itaconate, bis(S -isocyanato-2- butynyl)glutaconate, bis(7-isocyanato-4heptynyl) fumarate,bis(10-isocyanato-4-decynyl) glutaconate, bis(9-isocyanato-S-nonylyl)itaconate, bis(2-phenyl-3-isocyanatopropyl) fumarate,bis(3-naphthyl-5-isocyanatopentyl) fumarate,bis(3-styryl-5-isocyanatopentyl) glutaconate,bis(4-tolyl-6-isocyanatohexyl) itaconate, bis(6-cumcnyl-7-isocyanatoheptyl) glutaconate, bis(S-xylyl- 8 -isocyanatooctyl)fumarate, bis(7-mesityl-9-isocyanatononyl) glutaconate,bis(Z-cyclohexyl-3-isocyanatopropyl) itaconate,bis(3-cyclohexyl-5-isocyanatopentyl) fumarate, bis-(4-cyclohexyl-6-isocyanatohexyl) fumarate,bis(S-cyclohexylmethyl-7-isocyanatoheptyl) glutaconate,bis(3-cycloheptyl-S-isocyanatopentyl) itaconate, bis(3-cyclohexenyl-S-isocyanatopentyl) glutaconate,bis(S-cycloheptenylmethyl-8-isocyanatooctyl) fumarate, and the like.

In a second embodiment, attractive subclasses of novel esterdiisocyanates encompassed within Formula I supra are those wherein eachR represents a divalent cycloaliphatic group and which need not be thesame throughout the molecule and R has the same value as previouslyindicated. Preferred compounds within this embodiment are thoserepresented by Formula III below:

wherein R represents a divalent substituted or unsubstitutedcycloaliphatic group containing from 4 to 12 carbon atoms and R has thesame value as previously indicated. Particularly preferred compoundswithin this embodiment are those wherein R is a member selected from thegroup consisting of cycloalkylene, cycloalkenylene, cycloalkynylene,alkylcycloalkylene, alkylcycloalkenylene, alkylcycloalkynylene,alkylenecycloalkylene and cycloalkylenealkylene groups containing from 4to 10 carbon atoms and R is an alkenylene group containing from 2 to 24carbon atoms. The divalent cycloaliphatic group need not be the samethroughout the molecule.

Illustrative novel ester diisocyanates which are included in the secondembodiment are bis(Z-isocyanatocyclobutyl) fumarate,bis(3-isocyanatocyclopentyl) fumarate, bis(4-isocyanatocyclohexyl)glutaconate, bis(S-isocyanatocycloheptyl) itaconate, bis(7isocyanatocyclononyl) alpha-hydromuconate, bis(3-isocyanato-4-cyclopentenyl) beta-hydromuconate, bis(5-isocyanato-6-cycloheptenyl)fumarate, bis(6 isocyanato-7-cyclooctenyl) fumarate,bis(Z-isocyanatocyclobutylmethyl) glutaconate,bis(2-isocyanato-Z-ethylcyclobutyl) itaconate, bis[2(2'-isocyanatoethyl)cyclobutyl] fumarate, bis(3-isocyanatocyclopentylmethyl)fumarate, bis(3-isocyanato-2-ethylcyclopentyl) glutaconate,bis[3-(2-isocyanatoethyl)cyclopentyl] itaconate, bis5-isocyanatocycloheptylmethyl) fumarate,bis(3-isocyanato-S-methylcyclohexyl) fumarate,bis(3-isocynanato-5,6-dimethylcyclohexyl) glutaitaconate, and

conate, bis(3-isocyanato-4-ethylcyclopentyl)bis(3-isocyanato-4,S-diethylcyclopentyl) fumarate, the like.

In a third embodiment, highly desirable subclasses of novel esterdiisocyanates include those wherein each R (of Formula I) represents adivalent aromatic group which need not be the same throughout themolecule. Preferred compounds within this embodiment are represented byFormula IV infra:

wherein R represents a divalent substituted or unsubstituted aromaticgroup containing from 6 to 12 carbon atoms and R has the same value aspreviously indicated. Particularly preferred compounds within thisembodiment are those wherein R is a member selected from the groupconsisting of arylene, arylenealkylene, alkylenearylene, alkylarylene,arylenealkenylene and alkenylenearylene groups containing from 6 to 10carbon atoms and R is an alkylene group containing from 2 to 24 carbonatoms. The divalent aromatic groups need not be the same throughout themolecule.

Typical ester diisocyanates encompassed by the third embodiment includebis(4-isocyanatophenyl) fumarate, bis(2 isocyanatophenyl) fumarate,bis(3 isocyanatophenyl) glutaconate, bis(7-isocyanato-2-naphthyl)alphahydromuconate, bis(7-isocyanato-l-naphthyl) beta-hydromuconate,bis(4-isocyanato-4-biphenylyl) itaconate, bis (S-isocyanato-Z-indenyl)fumarate, bis(4 isocyanatobenzyl) fumarate, bis(4-isocyanatophenylethyl)glutaconate, bis(7-isocyanato 2 naphthylmethyl) itaconate,bis[4(3-isocyanatopropyl)phenyl] fumarate, bis(4-isocyanatomethylphenyl)fumarate, bis[2(3'-isocyanatopropyl)naphthyl] glutaconate,bis(4-isocyanato 2 methylphenyl) alphahydrornuconate,bis(6-isocyanato-2,4-xylyl) fumarate, bis(4-isocyanato-3-cumenyl)fumarate, bis(4- isocyanato 2 methoxyphenyl) glutaconate,bis(4-isocyanatostyryl) itaconate, bis(4-isocyanatocinnamyl) fumarate,bis[4(4-isocyanato 2' butenyl)phenyl] glutaconate, and the like.

The preferred novel ester diisocyanates are composed of carbon,hydrogen, oxygen, and nitrogen atoms. However, the novel diisocyanatescan also contain groups such as oxy, thio, polythio, sulfonyl, sulfinyl,carbonyloxy, nitro, cyano, halo, carbonate, and the like.

The novel ester diisocyanates can be produced in relatively high yieldsby novel processes which involve the reaction of the corresponding esterdiamine dihydrohalide starting material, contained in an inert,normally-liquid reaction medium, with a carbonyl dihalide, andthereafter recovering the ester diisocyanate product.

The starting materials for the production of the novel esterdiisocyanates of the present invention, as hereinbefore indicated, arethe corresponding olefinically unsaturated ester diamines or esterdiamine salts. The ester diamine salts can be conveniently representedby the following general formula:

wherein R and R have the same values as shown in Formula I above and HXrepresents hydrogen chloride, hydrogen bromide, or mineral acids such assulfuric, phosphoric, and the like. Other acid salts can also beutilized but inasmuch as hydrogen chloride has a common anion withphosgene it is the preferred salt, both from this, as well as economicconsiderations.

The preparation of the olefinically unsaturated ester diamines, andtheir hydrohalides, such as bis(Z-aminoethyl) fumarate,bis(Z-aminoethyl) fumarate dihydrohalide, bis(4-aminophenyl) fumaratedihydrohalide and the like is the subject matter of an applicationentitled Novel Amino Esters of Olcfinically Unsaturated PolycarboxylicAcids and Process For Preparation by T. K.

Brotherton and I. W. Lynn, Ser. 'No. 212,481, abandoned, filed July 25,1962, and assigned to the same assignee as the instant invention.

These diamino starting materials are prepared, as indicated in theexamples, and in the aforementioned copcnding application, by thereaction of an olefinically unsaturated polycarboxylic acid halide, suchas fumaroyl chloride, and a hydroxy amine hydrohalide, such asmonoethanolamine hydrohalide, at a temperature of from about 65 to about95 C. for several hours. The ester diamine dihydrohalide is thenisolated, as for example, by filtration and then washed and dried. Bythe aforementioned process the ester diamine dihydrohalides can beobtained in yields of about 95 percent and higher. For furtherinformation regarding the production of the ester diamines and theirhydrohalides reference is hereby made to the disclosure of theaforementioned application.

Eminently suitable starting materials which are useful in thepreparation of the novel diisocyanates illustrated by Formula II supraare shown in Formula VI below:

wherein R R and HX are as previously defined. Illustrative startingcompounds include the hydrohalide salts of the following olefinicallyunsaturated ester diamines: bis(2-aminoethyl) fumarate,bis(3-aminopropyl) glutaconate, bis(4-aminobutyl) alpha-hydromuconate,bis(5- aminopentyl) beta-hydromuconate, bis(7-aminoheptyl) itaconate,bis(2 methyl 3 aminopropyl) fumarate, bis (2,2-dimethyl-3-aminopropyl)fumarate, bis(3 -ethyl-5- aminopentyl) glutaconate,bis(3,4-diethyl-5-aminopentyl) alpha-hydromuconate, bis(4,4 dimethyl-6aminohexyl) beta-hydromuconate, bis(2-methyl-4-ethyl-6-aminohexyl)itaconate, bis(9-aminononyl) fumarate, bis(5,6,7triethyl- 9-aminononyl)fumarate, 2-aminoethyl 3-aminopropyl glutaconate, 3 aminopropyl 8aminooctyl beta-hydromuconate, 5 -aminopentyl 6 -aminohexyl itaconate,2- methyl-3-aminopropyl 3-aminoethyl fumarate, 4-ethyl-7- aminoheptyl 6aminohexyl fumarate, bis(4 amino 2- butenyl) glutaconate,bis(4-amino-2-butenyl) itaconate, bis(5-amino-3-pentenyl) fumarate,bis(7-amino-4-heptenyl) fumarate, bis(8 amino 4 octenyl) glutaconate,bis(9-amino-5-nonenyl) itaconate, bis(lO-amino-G-decenyl) fumarate,bis(3-ethyl-5-amino-3-pentenyl) fumarate,bis(3,4-dimethyl-5-amino-3-pentenyl) glutaconate, bis(2-methyl-4-ethyl-6-amino-2-hexenyl) itaconate, bis(5,6,7-triethyl-9-amino-4-nonenyl) fumarate, 4-amino-2-butenyl 3-aminopropylfumarate, 4-amino-2 butenyl 5-amino-3 pentenyl glutaconate,4-ethyl-7-amino-S-heptenyl 6-amino- 3-hexenyl itaconate,bis(5-amino-2-butynyl) fumarate, bis(7-amino-4-heptynyl) fumarate,bis(9-amino-5-nonynyl) itaconate, bis (Z-phenyl 3 aminopropyl) fumarate,bis(3-naphthyl-5-aminopentyl) fumarate, bis(3-styryl-5- aminopentyl)glutaconate, bis(4 tolyl 6 aminohexyl) itaconate,bis(6-cumenyl-7-aminoheptyl) fumarate, bis(5- xylyl-8-aminooctyl)fumarate, bis(7-mesityl 9 aminononyl) glutaconate, bis(2 cyclohexyl 3aminopropyl) itaconate, bis(3-cyclohexyl-S-aminopentyl) fumarate, bis(4-cyclohexyl-6-aminohexyl) fumarate,bis(S-cyclohexylmethyl-7-aminoheptyl) glutaconate, bis(3-cycloheptyl-5-aminopentyl) itaconate, bis(3 cyclohexenyl 5 aminopentyl)alpha-hydromuconate, bis(5-cycloheptenylmethyl- S-aminooctyl) fumarate,and the like.

Highly desirable ester diamine salts which can be used for thepreparation of the novel ester diisocyanates illustrated by Formula IIIsupra can be represented by Formula VII below:

VII II II HX-NH2R -OCR1COR3NHz-HX wherein R R and HX are as previouslydefined. Illustrative diamino starting materials include thedihydrohalide salts of the following: bis(Z-aminccyclobutyl) fumarate,bis(3 aminocyclopentyl) fumarate, bis(4- aminocyclohexyl) glutaconate,bis(S-aminocyeloheptyl) itaconate, bis(7-amin0cyclononyl)alpha-hydromuconate, bis(3-amino-4-cyclopentenyl) beta-hydromuconate,bis(5- amino-6-cycloheptenyl) fumarate, bis(6-amino-7-cyclooctenyl)fumarate, bis(2-aminocyclobutylmethyl) glutaconate,bis(2amino-2-ethylcyclobutyl) itaconate, bis[2(2'-aminoethyl)cyclobutyl] fumarate, bis(3-aminocyclopentylmethyl)fumarate, bis(3-amino-2-ethylcyclopentyl) glutaconate, bis[3(2-aminoethyl)cyclopentyl] itaconate, bis(S-aminocycloheptylmethyl)fumarate, bis(3-amino-5- methylcyclohexyl) fumarate,bis(3-amino-5,6+limethylcyclohexyl) glutaconate,bis(3-amino-4-ethylcyclopentyl) itaconate,bis(3-amino-4,S-diethylcyclopentyl) fumarate, and the like.

The novel ester diisocyanates exemplified by Formula IV supra can beprepared from the corresponding ester diamine salts having the formula:

VIII

wherein R R and HX have the same values as previously indicated.Examples of such diamine compounds include the dihydrohalide salts of:bis(4-aminophenyl fumarate, bis(2-aminophenyl) fumarate, bis(3-aminophenyl) glutaconate, bis(7-amino-2-naphthyl) alphahydromuconate, bis(7 amino1 naphthyl) beta-hydromuconate, bis(4 amino 4 biphenylyl) itaconate,bis(S-amino-Z- indenyl) fumarate, bis(4-aminobenzyl) fumarate, bis(4-aminophenylethyl) glutaconate, bis(7-amino-2-naphthylmethyl) itaconate,bis[4(3-aminopropyl)-phenyl] fumarate, bis(4-aminomethylphenyl)fumarate, bis[2(3'- aminopropyl) naphthyl] glutaconate, bis4-amino-2-methylphenyl) alpha-hydromuconate, bis(6-arnino-2,4-xylyl)fumarate, bis(4-amino-3-cumenyl) fumarate, bis(4-amino- 2-methoxyphenyl)glutaconate, bis(4-aminostyryl) itaconate, bis(4-aminocinnamyl)fumarate, bis[4(4-amino- 2-butenyl)phenyl] glutaconate, and the like.

In general, the conversion of the ester diamine or ester diamine saltreactants to the novel ester diisocyanate is accomplished by contactinga carbonyl dihalide, more preferably, by sparging phosgene, through aslurry of the ester diamine or the ester diamine dihydrohalide containedin an inert, normally liquid organic medium at a temperature within therange of from about C., and lower to about 225 C., more preferably fromabout C. to about C., and thereafter recovering the novel esterdiisocyanate. In either instance, it is believed that the intermediatecarbamoyl chloride is first formed from the free amine and subsequentlythermally degraded to the diisocyanate at the reaction temperatureemployed. The process can be conducted in either a batch type orcontinuous reactor.

In general, the liquid reaction medium employed in the conversion of theester diamine or ester diamine salt to the corresponding novel esterdiisocyanate should be inert t0 the reactants and stable under theconditions employed. Moreover, it should be easily separable from theresulting ester diisocyanate. Typical inert, liquid media which havebeen found suitable for utilization in the process of the presentinvention include, among others, the aromatic hydrocarbons such astoluene, xylene, naphthalene, tetrahydronaphthalene, benzene, biphenyl,cumene, amylbenzene; the cycloaliphatic hydrocarbons such ascyclohexane, heptylcyclopentane, decahydronaphthalene; the chlorinatedaromatic hydrocarbons such as chlorobenzene, ortho-dichlorobenzene,1,2,4-trichlorobenzene; the chlorinated aliphatic hydrocarbons such ascarbon tetrachloride, tetrachloroethylene, trichloroethylene; thedialkyl ketones such as diisobutyl ketone, methyl isobutyl ketone,methyl hexyl ketone, diisopropyl ketone; and other organic media such astetramethylene sulfone, and the like.

Although reaction temperatures within the aforementioned range of fromabout 100 C. to about 225 C., have been found desirable, temperaturesabove and below this range can also be employed. However, from economicconsideration the optimum yield and rate of reaction are attained withinthe aforesaid range. The particular temperature employed will bedependent, in part, upon the ester diamine or ester diamine saltstarting material. Moreover, the optimum temperature for the conversionof the diamino reactant to the novel ester diisocyanate is influenced,to a degree, by other reaction variables. For instance, in a batch typereactor with ortho-dichlorobenzene as the inert reaction medium, anamine hydrohalide concentration of -25 weight percent, based on theweight of the medium, and a phosgene feed rate of 0.5 to mols per mol ofamine hydrohalide per hour, the optimum temperature range is from about125 C. to about 170 C. At temperatures below 125 C., the reaction timeswere too long to be practical, while at temperatures above 170 C. thediisocyanato product was, in part, converted to resinous materials.

The pressure is not critical and the novel processes can be conducted atatmospheric, subatmospheric, and superatmospheric pressures.

Although the novel processes preferably are conducted with phosgene, inits broadest concept the process includes the utilization of anycarbonyl dihalide such as carbonyl difluoride, or carbonyl dibromide.However, for economic consideration phosgene is the preferred carbonyldihalide. In the preparation of the novel diisocyanates, phosgene can beused in either the gaseous or liquid form.

Inasmuch as the yield and rate of information of the novel esterdiisocyanate product are dependent upon several variables, for example,concentration of the ester diamino reactant, solubility of the esterdiamino reactant and phosgene in the reaction medium, reactiontemperature, pressure, and rate of addition of the phosgene, no hard andfast rule can be devised regarding the optimum conditions to be employedin practicing the novel processes.

In a preferred embodiment of the present process the ester diaminedihydrohalide is slurried in 1,2,4-trichlorobenzene. Thereafter, gaseousphosgene is then sparged through the reaction mixture at a temperaturewithin the aforesaid range and for a period of time to essentiallycomplete the reaction. After removal of the hydrogen chloride by-productand the chlorinated benzene a crude diisocyanate product is obtainedwhich is refined by known purification techniques such as distillation,recrystallization, washing, and the like.

In practice, it has been found that the mol ratio of phosgene to esterdiamine dihydrohalide in the initial reaction medium preferably shouldbe in excess of 3:1, although satisfactory results have been obtained ata lower ratio. When the phosgene subsequently is sparged into thereaction medium feed rates of up to about 10 mols of phosgene per mol ofamine per hour are preferred, although higher rates can equally as Wellbe employed.

The novel diisocyanates are an extremely useful class of compounds whchpossess exceptionally attractive and outstanding properties. Thereaction products of the novel aliphatic diisocyanates are highlyresistant to sunlight or ultra-violet light degradation. For example,the use of the novel diisocyanates as the isocyanate source in thepreparation of, for example, polyurethane films, elastic, and relativelynon-elastic fibers, coatings, cast elastomers, etc., results innon-yellowing products which have strong commercial appeal as well asperformance characteristics. It should be noted that non-yellowingelastomeric and non-elastomeric thread or fiber are in great demandwithin the industry since the commercial products based on aromaticisocyanates rapidly turn yellow in sunlight. The novel diisocyanatessuch as bis(Z-isocyanatoethyl) fumarate,bis[(2-isocyanato-l-methyl)ethyl] fumarate, and others, arenon-lachrymators which possess relatively little or no odor at ordinaryworking temperatures and thus allows for their use without the need forspecial venting systems and/or face masks. On the other hand, bothtolylene diisocyanate, the largest volume commercial diisocyanate, andhexamethylene diisocyanate, the only aliphatic diisocyanate currentlyavailable in commercial quantities, are extremely strong lachrymators.

Isocyanates, as a class, should be considered to be toxic materials withrelative orders of toxicity. Using tolylene diisocyanate andhexamethylene diisocyanate as the yardsticks, the following has beenobserved. Toxicity by skin absorption: (a) hexamethylene diisocyanatehigh toxicity; (b) tolylene diisocyanatemoderate toxicity; (c) bis(Zisocyanatoethyl) fumarate and bis[(2 isocyanato-l-methyl)ethyl]fumarate-extremely low toxicity. Skin sensitization tests: (a)hexamethylene diisocyanate and tolylene diisocyanate-severe sensitizers;(b) bis(2-isocyanatoethyl) fumarate andbis[(2-isocyanato-l-methyl)ethyl] fumarateextremely mild sensitizers. Itshould be noted that the practical utility of hexamethylene diisocyanatehas been severely limited because of its extremely high toxicity.

With the exception of the highly expensive vinylene diisocyanate (whichis an extremely potent lachrymator and undoubtedly highly toxic), thenovel diester diisocyanates such as bis(Z-isocyanatoethyl) fumarate,bis[(2 isocyanato-1-methyl)ethyl] fumarate, and other diisocyanatesencompassed within Formula I supra, appear to be the only known and/oravailable aliphatic diisocyanates which can undergo polymer formingreactions by both true vinyl polymerization and isocyanate condensationpolymerization routes.

Many of the novel diisocyanates such as bis(2-isocyanatoethyl) fumarateand bis[(2-isocyanato-1-methyl)- ethyl] fumarate are relativelyinexpensive compounds which can readily compete with tolylenediisocyanate on a commercial scale. Based on presently known processesfor preparing vinylene diisocyanate, this latter diisocyanate isdefinitely not competitive (on an economic basis) with theafore-illustrated novel diisocyanates. Moreover, as indicatedpreviously, vinylene diisocyanate is a potent lachrymator andundoubtedly highly toxic which characteristics place severe limitationson its acceptance and applicability.

Of outstanding importance and utility with regard to the noveldiisocyanates is their ability to undergo true vinyl polymerization andisocyanate condensation polymerization. For example, the noveldiisocyanates can be homopolymerized or copolymerized with a host ofethylenically unsaturated compounds, e.g., styrene, vinyl chlo ride,butadiene, isoprene, chloroprene, ethyl acrylate, methyl acrylate, etc.,through the ethylenic bond of the reactant(s), under conventional vinylpolymerization conditions, to give polymers of varying molecular weightwhich contain a plurality of pendant or free isocyanate groups. Thefollowing specific equation which is not to be construed as limiting inscope illustrates the overall reaction:

wherein n is a number having a value greater than one and upwards toseveral hundred, e.g., from two to 200, and higher and wherein C Crepresents an ethylenieally unsaturated organic compound which containsat least one polymerizable ethylenic bond, e.g., vinyl chloride,butadiene, etc. The resulting polyisocyanato-containing polymers thencan be subjected to isocyanate condensation polymerization reactionswith an active polyhydrogen compound, e.g., polyol. polyamine, etc., asexplained hereinafter to give useful three dimensional, crosslinkedsolid products which can be termed poly(vinyl urethanes),

poly(vinyl ureas), etc., depending on the active hydrogen compoundemployed.

The reaction of the novel diisocyanates of Formula 1 supra, on the otherhand, with an active monohydrogen compound, e.g., monoamine, alkanol,etc., results in novel ethylenically unsaturated compounds which in turncan be polymerized with an ethylenically unsaturated organic compoundwhich contains at least one polymerizable 'ethylenic bond, e.g., theso-called vinyl monomers,

through the polymerizable carbon to carbon double bond, to yield amyriad of polymeric products. The following equations are illustrativeof typical reactions:

0 linear poly( vinyl urethanes) o CO2C2H4NH%NHR FDI-l-ZRNHz CH=CHCOzUzHrNHNHR linear poly(vinyl ureas) CH2=CHC1 FDI HOROH linenearpolyurethanes films and fibers, thermoplastic resins, cast resins, etc.,possess, among other things, outstanding and exceptionalcharacteristics. Bis-(2-isocyanatoethyl) fumarate (hereinafterdesignated as FDI) possesses the following properties: molecularweight254; 71 -1462}; melting point52 011 C.; boiling pointabout 152C./0.2 mm. of Hg; appearancecrystalline solid; solubilitysoluble in mostof the common organic solvents, e.g., hexane, heptane, benzene,chlorobe'nzene, toluene, etc. Bis(2 -isocyanato-l-methylethyl) fumarate(hereinafter designated as LIFDI), on the other hand, is a very mobile,water-white liquid, a characteristic which cannot be overemphasized inisocyanate and urethane chemistry as witnessed by the huge success oftolylene diisocyanate (TDI). Further properties of LIFDI include thefollowing: molecular weight-282; n --1.47l9; boiling point144-145C./0.15 mm. of Hg; and solubility characteristics similar to that ofFDI.

Of the several monoand polyisocyanates (excluding the aforesaid vinylenediisocyanate) published in Annalen, 562, pages 122-135 (1949), the onlyaliphatic diisocyanate which contained a carbon to carbon double bondwas Z-butenylene diisocyanate,

OCNCH CH=CHCH NCO As is well documented in the literature, olefiniccompounds which contain allylic hydrogen are not considered to be truevinyl monomers in a practical sense. The aforesaid diisocyanate fallsinto this category.

US. Pat. No. 2,797,232, issued June 25, 1957, is directed to thepreparation of so-called hidden polyisocyanates which are obtained viathe reaction of hydroxyalkyl-carbamic acid-aryl esters withpolycarboxylic acids. These hidden polyisocyanates upon heating totemperatures above 150 C., are purported to yield free polyisocyanates.In accordance with the patentees disclosure, various attempts were madeto prepare free polyisocyanate from the hidden polyisocyanate in theapplicants laboratory. Firstly, the decomposition or thermal degradationof the reaction product of phenyl N-(2-hydroxyethyl) carbamate (termedby the patentee as hydroxyethyl-carbamic acid-phenyl ester) and maleicacid anhydride (the sole ethylenically unsaturated acid, anhydride, oracyl halide disclosed by the patentee), i.e., the purported hiddenpolyisocyanate, failed to result in 'any recoverably free diisocyanate.In lieu of maleic acid anhydride, the applicants then employed maleicacid,

diolefinic compound crosslinked poly(vinyl urethanes) Crosslinkedpoly(vinyl urethanes) can also be prepared via a one-shot process whichinvolves concurrent vinyl and condensation polymerization reactions, forexample:

FDI+HOROH+ CH CHCl crosslinked poly (vinyl urethanes) Thus, it isapparent that the novel polyisocyanates permit the wedding of low costvinyl monomers, i.e., ethylenically unsaturated organic monomers whichcontain at least one polymerizable ethylenic bond, with high performancepolyurethanes, polyureas, and the like. This advantage has outstandingsignificance in the development of a myriad of products (based on thenovel diisocyanates) which have exceptionally strong commercial andeconomic attractiveness.

Of the novel diisocyanates, the bis(omega-isocyanatoalkyl) fumaratesdeserve special mention. Of these, bis- (2-isocyanatoethyl) fumarate(FDI) and bis(2-isocyanato-l-methylethyl) fumarate (LIFDI) are of highsignificance since products made therefrom, e.g., elastic fumaroylchloride, succinic acid, and adipic acid in the above experiments.Failure to produce any recoverable free diisocyanate was encountered ineach instance. These experiments were effected with meticulous care,using sophisticated chemical techniques. Applicants operative Examples23 through 26 in this specification emphatically and unequivocallyestablish that by following the teachings of US. Pat. 2,797,232, usingthe most optimum conditions and sophisticated chemical techniques, norecoverable free diisocyanate is obtained from the thermal degradationor decomposition of the hidden polyisocyanate, i.e., the reactionproduct of phenyl N-(Z- hydroxyethyl) carbamate with maleic acidanhydride, maleic acid, fumaroyl chloride, succinic acid, or adipicacid. It should be noted, in passing, that maleate compounds are, ingeneral, sluggish vinyl monomers when compared with fumarate monomers.

In one aspect, the invention is directed to the preparation of novelmultifunctional polymers of the novel diison' t lonNco wherein R has thevalues set out in Formula I supra, wherein R is a divalent saturatedaliphatic radical which preferably contains up to 22 carbon atoms, andwherein m is an integer which has a value of zero or one. Moreparticularly, the novel polymers are characterized by Unit IX below:

wherein R" is a tetravalent saturated aliphatic which possesses two (andonly two) carbon atoms in the polymeric chain, wherein each R is adivalent saturated aliphatic radical, wherein each m is an integerhaving a value of zero or one, wherein the moiety preferably contains upto 24 carbon atoms and preferably still, up to carbon atoms, whereineach R has the values enumerated in Formula I supra; with the provisosthat (1) each isocyanato moiety (NCO) of the above unit is at least twocarbon atoms removed from the oxycarbonyl moiety and (2) eachisocyanatohydrocarbyloxycarbonyl moiety, i.e.,

ll OCNROC generic manner are characterized by Unit IXA below:

IXA g R o l li i J OCNROC-R RCORNCO fa Jm wherein the variables R", R,R, and 111 have the meanings set out in Unit IX supra (including thegeneral and preferred values as well as the provisos), wherein R is asubstituted or unsubstituted divalent radical which contains two carbonatoms in the polymeric chain (R in effect, is the polymerizablecomonomer which enters into chemical union with the other monomer(s)through the polymerizable ethylenic bond), and wherein x has a value ofzero or one.

A highly desirable subarea of novel polyisocyanatocontaining polymerswhich deserve special mention are characterized by Unit IXB below:

wherein the variables R, R R, m, and x have the values noted in Unit IXAsupra.

Those novel polyisocyanato-containing polymers which contain at leastone of, preferably a plurality of, the structure defined as Unit IXCbelow, represent a significant contributionto the art, to wit:

IXC (I? I CORNCO CHCII (HDORNCOJ wherein R is an alkylene radical whichpreferably contains from 2 to 12 carbon atoms. It is preferred that thestructure defined as Unit IXC represent a repeating unit such that thenovel polymer is characterized by at least two and upwards to 200, andhigher, of Unit IXC therein. It is further preferred that the R radicalbe ethylene, trimethylene, tetramethylene, methyl substituted ethylene,or methyl substituted trimethylene.

Novel polymers characterized by one or more (and upwards to 200, andhigher) of Unit IXD below represent a highly important embodiment of theinvention,

that is:

it CORNCO wherein R has the broad and preferred values set out in UnitIXC supra, and wherein R and x have the values noted in Unit IXA supra.

Illustrative polymers characterized by the presence of the aforesaidrecurring unit include the homopolymers 0f thebis(isocyanatohydrocarbyl) fumarates as exemplified by thepoly[bis(omega-isocyanatoalkyl) fumarates] such aspoly[bis(2-isocyanatoethyl) fumarate]poly[bis(2-isocyanato-l-methylethyl) fumarate], poly [bis( 3-isocyanatonpropyl) fumarate], poly[bis(3 isocyanato-methylpropyl) fumarate],poly[bis(4-isocyanato-n-butyl) fumarate], and the like; the copolymersof the bis(isocyanatohydrocarbyl) fumarate with other ethylenicallyunsaturated organic compounds as illustrated by the copolymers of (1)the bis(omega-isocyanatoalkyl) fumarates such as bis(2 isocyanatoethyl)fumarate, bis(2-isocyanato-1- methylethyl) fumarate,bis(3-isocyanato-n-propyl) fumarate, bis(3-isocyanato-methylpropyl)fumarate, bis- (4-isocyanato-n-butyl) fumarate, and the like; and (2)other ethylenically unsaturated organic compounds such as styrene, vinylchloride, vinylidene chloride, methyl acrylate, vinyl methyl ether,methyl methacrylate, 2- ethylhexyl acrylate, vinyl acetate, and/or thediisocyanates of Formula I supra, and the like.

As hereinbefore indicated, the novel polymers of the instant inventionare obtained by effecting polymerization of the novel diisocyanatethrough an ethylenic group. As a result, each of the polymers obtainedis characterized by pendant isocyanato-terminated ester groups along thepolymer chain. Depending upon the amount of polymerizable noveldiisocyanate employed with other vinyl monomers, the copolymers obtainedin accordance with the teachings of this aspect have a wide variety ofuseful properties and applications. For example, copolymerization of amixture of styrene, 2-ethylhexylacrylate, and bis(2-isocyanatoethyl)fumarate, in a weight ratio of 45:50:5, furnished a soft, flexible film.In contrast, when the copolymerization was conducted in the same mannerwith the respective monomers in a ratio of 70:25:5 the resultingpolymeric film was hard and exhibited little tendency to bend. Inaddition, by virtue of the highly reactive pendant isocyanato groups,the polymers can be further reacted with active hydrogen-containingcom.- pounds to form other novel products useful as coatings, adhesives,castings, foams, and the like.

It is pointed out at this time that the term polymer(s) is used in itsgeneric sense, i.e., this term encompasses within its scope polymersprepared from a sole novel diisocyanate as well as a mixture containingtwo, three, four, etc., polymerizable monomers, at least one of which isa novl diisocyanate. Thus, homopolymers and copolymers are encompassedwithin the term polymer. Each of the polymerizable monomers enteringinto the copolymerization reaction do so in significant quantities. Assuch, the resulting copolymeric products can be chemicallydistinguishable from the homopolymeric products which would result fromthe homopolymerization of the monomers separately.

A distinguishing feature of the copolymeric materials is that at leastone of the monomers from which the copolymers are made has both anisocyanate portion and an olefinically unsaturated portion. In addition,the polymers can contain one or more vinyl monomers chemically combinedtherein. In general, the concentration of the polymerizable monomerschemically combined in the novel polymers can vary over the entirerange, e.g., from about 0.5, and lower, to about 99.5 weight percent andhigher of the polymerizable reactants chemically combined therein, basedon the total weight of said reactants. Those copolymers which contain atleast 50 weight percent of vinyl monomer, based on the weight of saidpolymer, are highly preferred. Those copolymers which contain at leastabout 50 to about 97 weight percent vinyl monomer, and from about 50 toabout 3 weight percent ester diisocyanate are eminently preferred.

The novel polymers can be prepared by reacting an admixture comprisingnovel diisocyanate(s) with/without a vinyl momoner(s) plus acatalytically significant quantity of a vinyl polymerization catalyst,particularly the free radical producing catalysts, under conventionalvinyl polymerization conditions.

The free radical producing catalysts are voluminously documented in theart and well known to those skilled in the vinyl polymerization art.Illustrative thereof are those compounds which contain the divalent OO'-unit as exemplified by 1) ROOR wherein R is alkyl, aryl, haloaryl, acyl,etc.; (2) RO-OH wherein R is a nonacyl radical such as hydrogen, alkyl,etc.; (3) ROOH wherein R" is acyl; (4) the azo-compounds; and the like.Specific illustrations include, among others, hydrogen peroxide,dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, t-butylhydroperoxide, di-t-butyl peroxide, lauroyl peroxide, butyryl peroxide,dicumyl peroxide, azo-bis-isobutyronitrile, the persulfates,percarbonates, perborates, peracids, etc., such as persuccinic acid,diisopropyl peroxydicarbonate, t-butyl perbenzoate, di-t-butyldiperphthalate, peracetic acid, and the like. Ionic catalysts such asboron trifluoride and anionic catalysts such as sodium phenyl may alsobe employed in certain cases.

The catalysts are employed in catalytically significant quantities. Ingeneral, a catalyst concentration in the range of from about 0.001, andlower, to about 10, and higher, weight percent, based on the weight oftotal monomeric feed, is suitable. A catalyst concentration in the rangeof from about 0.01 to about 3.0 weight percent is preferred. For optimumresults, the particular catalyst employed,

the nature of the monomeric reagent(s), the operative conditions, underwhich the polymerization reaction is conducted, and other factors willlargely determine the desired catalyst concentration.

The vinyl polymerization reaction can be conducted at a temperature inthe range of from about 0, and lower, to about 200 C., and higher,preferably from about 20 C. to about 150 C. As a practical matter, thechoice of the particular temperature at which to effect thepolymerization reaction depends, to an extent, on the variablesillustrated above. The reaction time can vary from several seconds toseveral days. A feasible reaction period is from about a couple ofhours, and lower, to about hours, and longer. Preferably, the reactiontakes place in the liquid phase.

The vinyl polymerization can, if desired, be carried out in an inertnormally liquid organic vehicle. The suitable inert vehicles arepreferably those which do not react with either the polymerizablemonomer or the ester diisocyanate. In view of the reactivity ofisocyanato groups with labile hydrogen-containing materials, thepreferred vehicles for the polymerization are those which do not possessactive hydrogens or contain impurities which possess active hydrogens.Illustrative vehicles which may be satisfactorily used are the aromatichydrocarbons such as toluene, xylene, naphthalene,tetrahydronaphthalene, benzene, biphenyl, cymene, amylbenzene; thecycloaliphatic hydrocarbons such as cyclohexane, cyclopentane,decahydronaphthalene; the dialkyl ketones such as acetone, diisobutylketone, methyl isobutyl ketone, diisopropyl ketone, the organic esterssuch as ethyl acetate, and other inert, normal-liquid, organic vehicles.

The molar ratio of polymerizable reactants to vehicle is notparticularly critical, and it can vary, for example, from about 1:1, andlower, to about 1:1000, and higher. In general, it is desirable toemploy a molar excess of organic vehicle.

The polymerizable monomers used in the copolymerization reaction withthe novel ester diisocyanates are preferably the ethylenicallyunsaturated organic compounds which are free of reactive hydrogen atomsas determined according to the Zerewitinoff test and which will notreact with the isocyanato group. These compounds can be used singly orin combinations of two or more and are characterized by the presencetherein of at least one polymerizable ethylenic group of the type C=CThese compounds are well known in the art and include, for example, thealkenes, alkadienes, and the styrenes such as ethylene, propylene,l-butylene, Z-butylene, isobutylene, l-octene, butadiene, isoprene,1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene,alphamethylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene,vinylcumene, 1,5- cyclooctadiene, cyclohexene, cyclooctene,benzylstyrene, chlorostyrene, bromostyrene, fluorostyrene,trifluoromethylstyrene, iodostyrene, cyanostyrene, nitrostyrene, N,N-dimethylaminostyrene, acetoxystyrene, methyl 4-vinylbenzoate,phenoxystyrene, p-vinylphenyl ethyl ether, and the like; the acrylic andsubstituted acrylic monomers such as methyl acrylate, ethyl acrylate,methyl methacrylate, methacrylic anhydride, acrylic anhydride,cyclohexyl, methacrylate, benzyl methacrylate, isopropyl methacrylate,octyl, methacrylate, acrylonitrile methacrylonitrile, methylalpha-chloroacrylate, ethyl alpha-ethoxyacrylate, methylalpha-acetamidoacrylate, butyl acrylate, ethyl alpha-cyanoacrylate,2ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate,alpha-chloroacrylonitrile, N,N- dimethylacrylamide,N,N-dibenzylacrylamide, N-butylacrylamide, methacrylyl formamide, andthe like; the vinyl esters, vinyl halides, vinyl ethers, vinyl ketones,etc. such as vinyl acetate, vinyl chloroacetate, vinyl butyrate,isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate,vinyl methoxy acetate, vinyl benzoate, vinyl iodide, vinyl chloride,vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene cyanide,vinylidene bromide, l-chloro-l-fluoroethylene, vinylidene fluoride,vinyl methyl ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butylethers, vinyl Z-ethylhexyl ether, vinyl phenyl ether, vinyl2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether,3,4-dihydro-l,2-pyran, 2-butoxy-2'-vinyloxy diethyl ether, vinyl2-ethylmercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone,vinyl phenyl ketone, vinyl ethyl sulfide, vinyl ethyl sulfone,N-vinyloxazolidinone, N-methyl-N-vinyl acetamide, N-vinylpyrrolidone,vinyl imidazole, divinyl sulfide, divinyl sulfoxide, divinyl sulfone,sodium vinyl sulfonate, methyl vinyl sulfonate, N-vinyl pyrrole, and thelike; dimethyl fumarate, vinylisocyanate, tetrafluoroethylene,chlorotrifluoroethylene, nitroethylene, and the like.

As indicated previously, the novel polyisocyanato-containing polymerscan contain as many as 200, or more, of the units designated as Units IXthrough IXD supra. In general, these polymers are in the solid range,and they are substantially linear and non-crosslinked. In an exceedinglyimportant embodiment there can be prepared relatively low molecularweight polymeric aliphatic multiisocyanates, many of which are pourable,i.e., liquid. In particular, the relatively low molecular weightpolymers of bis[omega-isocyanato(C C alkyl)] fumarates and substitutedfumarates deserve special mention in view of their commercialattractiveness in preparing non-yellowing rigid urethane foams, castresins, thermoplastic resins, coatings, etc., which have highperformance characteristics. Polymers of bis(2-isocyanatoethyl) fumarateand bis(2-isocyanato-1-methylethyl) furnarate are preferred. Theserelatively low molecular polyisocyanato-containing polymers arecharacterized by the recurring unit identified as Unit IXC supra, or amixture of recurring units which fall within the scope of Unit IXCsupra. Other vinyl monomers such as styrene, vinyl chloride, vinylidenechloride, vinyl acetate, ethylene, methyl acrylate, etc., may also becopolymerized with the bis[omega-isocyanato(C -C alkyl)] fumarates toyield relatively low molecular weight polyisocyanato-containingpolymers.

The aforesaid relatively low molecular weight polymers can be preparedvia the vinyl polymerization routes discussed previously, using a freeradical producing catalyst as illustrated supra, e.g., a compound whichcontains the unit -OO, under the operative conditions set out above. Itwill be necessary, however, in the preparation of these telomers or lowmolecular weight polymers to employ a normally-liquid organic solventwhich possesses a relatively high, transfer agent constant asillustrated by the polyhalogenated lower alkanes, e.g., chloroform,carbon tetrachloride, iodiform, bromoform, pentachloroethane, and thelike; the various allylic compounds of the type CH CHCH X (the variableX being, for instance, halogen), and the like. The aforesaid exemplifiedsolvents do not contain functional groups which are reactive withisocyanato groups under the conditions employed. Carbon tetrachloride isthe preferred transfer agent. The concentration of the organic solventis of the order described previously for the inert organic vehicles.

The aforesaid relatively low molecular weight polyisocyanato-containingpolymers may more properly be termed telomers since examination thereofhas shown the presence of the telogen (the normally liquid organicsolvent) therein. In general, as the preferred telogens are thehalogenated aliphatic hydrocarbons, the resulting telomers may becharacterized by fragments of the telogen at the terminal sites of thepolymeric molecule. For example, with carbon tetrachloride as theorganic solvent of choice, the carbon tetrachloride acts in a mannersomewhat similar to a chain stopper. Thus, the resulting telomer can becharacterized with a chloride fragment and a trichloromethyl fragment atthe terminal sites of the polymeric chain thereof. As a rule of thumb,if the telogen is represented by RX wherein X is halo such as chloro,bromo, etc., and R is a monovalent aliphatic hydrocarbon radical or a.monovalent monoor polyhalogenated hydrocarbon radical such as alkyl, thechlorinated alkyls, etc., the resulting telomer may be considered topossess the R and X fragments (of the telogen) at the terminal sites ofthe polymeric molecule.

To a significant degree, the diisocyanate(s) of choice, the organicsolvent or telomer of choice, the concentration of the diisocyanate(s)and organic solvent, the purity of the diisocyanate(s), etc., willlargely influence the resulting molecular weight of the polymer.Consequently, it will be necessary to one having ordinary skill in theart to correlate, in a routine fashion, the various variablesillustrated above as well as the vinyl polymerization operativeconditions in order to obtain the desired polyisocyanato-containingpolymeric products.

The novel relatively low molecular polymers which result from thisembodiment have average molecular weights ranging up to about 5000, andpreferably up to about 2500. These polymers are characterized in thatthey contain from 2 to about 20, preferably from 3 to about 10, of theunits designated as Unit IXC supra.

Of particular importance are the telomers of his- [omega-isocyanato(C Calkyl)] fumarates, citraconates, and itaconates, and especially thosewhich have the recurring units, respectively:

r w |CO CHCHzNCO (IIJO |CI-ICHzNCOJ O CH: X

wherein x equals 2 to about 20, preferably from 3 to about 10.

In one aspect, the invention is directed to the preparation of novelproducts which result from the reaction of the novel polyisocyanatessuch as those exemplified by Formula I and Units IX through IXF supraand other novel polyisocyanates exemplified hereinafter with compoundswhich contain at least one reactive hydrogen as determined according tothe Zerewitinoff test described by Wohler in the Journal of the AmericanChemical Society, volume 48, page 3181 (1927). Illustrative classes ofcompounds which contain at least one active hydrogen include, forinstance, alcohols, amines, carboxylic acids, phenols, ureas, urethanes,hydrazines, water, ammonia, hydrogen sulfide, imines, thioureas,sulfimides, amides, thiols, amino alcohols, sulfonamides, hydrazones,semicarbazones, oximes, hydroxycarboxylic acids, aminocarboxylic acids,vinyl polymers which contain a plurality of pendant active hydrogensubstituents such as hydroxyl or amino, and the like. In addition, thehydrogen substituent may be activated by proximity to a carbonyl group.The active hydrogen organic compounds represent a preferred class.

Illustrative of the aforesaid active hydrogen compounds are thehydroxyl-containing compounds, especially those which possess at leastone alcoholic hydroxyl group and preferably at least two alcoholichydroxyl groups. Typical compounds include, for instance, the monohydricalcohols such as methanol, ethanol, propanol, isopropanol, l-butanol,allyl alcohol, 2-butanol, tert-butanol, 3-butenol, l-pentanol,3-pentanol, l-hexanol, hex-S-en-l-ol, 3-heptanol, 2-ethyl-l-hexanol,4-nonanol, propargyl alcohol, benzyl alcohol, cyclohexanol,cyclopentanol, cycloheptanol, and trimethylcyclohexanol. Furtheralcohols contemplated include glycidol, 4-oxatetracyclo[6.2.1.0 0undecan-9-ol, and the monoesterified diols such as those l7 prepared bythe reaction of equimolar amounts of an organic monocarboxylic acid, itsester, or its halide, with a diol such as alkylene glycols, monoandpolyether diols, monoand polyester diols, etc., e.g.,

II R G O ROH wherein H RC is acyl and R is a divalent organic radicalcontaining at least two carbon atoms in the divalent chain; themonoetherified diols such as those represented by the formula R OROHwherein R represents a monovalent organic radical such as a hydrocarbylor oxahydrocarbyl radical and R has the aforesaid value; the mono-01sproduced by the partial esterification reaction of a polyol containingat least three hydroxyl groups, e.g., glycerine, with a stoichiometricdeficiency of an organic monocarboxylic acid, its ester, or acyl halide;and the like. The aforesaid reactions are well documented in theliterature.

Polyhydric alcohols can be exemplified by polyols of the formula HO-ROHwherein R is a divalent hydrocarbyl radical and preferably a substitutedor unsubstituted alkylene radical, the aforesaid formula hereinafterbeing referred to as alkylene glycols; or by the formula HO'R'OH whereinR is a substituted or unsubstituted (alkyleneoxy) alkylene radical withn being at least one, this latter formula hereinafter being referred toas polyether glycols. The variables R and R have at least two carbonatoms in the linear chain, and the substituents or pendant groups onthese variables can be, for example, lower alkyl, halo, lower alkoxy,etc., such as methyl, ethyl, n-propyl, isopropyl, chloro, methoxy,ethoxy, and the like. Illustrative alkylene glycols and polyetherglycols include ethylene glycol, propylene glycol; butylene glycol;2,2-dimethyl-1,3-propanediol; 2,2-diethyl- 1,3-propanediol;3-methyl-1,5-pentanediol; 2-butene-l,4- diol; the polyoxyalkyleneglycols such as diethylene glycol, dipropylene glycol, dibutyleneglycol, polyoxytetramethylene glycol, and the like; the mixed monoandpolyoxyalkylene glycols such as the monoand polyoxyethyleneoxypropyleneglycols, the monoand polyoxyethyleneoxybutylene glycols, and the like;polydioxolane and polyformals prepared by reacting formaldehyde withother glycols or mixtures of glycols, such as tetramethylene glycol andpentamethylene glycol; and the like. Other polyols include theN-methyland N-ethyl-diethanolamines; 4,4'-methylenebiscyclohexanol;4,4-isopropylidenebiscyclohexanol; butyne-1,4-diol; the ortho-, meta-,and para-xylene glycols; the hydroxymethyl substituted phenethylalcohols; the ortho-, meta-, and para hydroxymethylphenylpropanols; thevarious phenylenediethanols, the various phenylenedipropanols, thevarious heterocyclic diols such as 1,4-piperazine diethanol; and thelike. The polyhydroxyl-containing esterification products which rangefrom liquid to non-crosslinked solids, i.e., solids which are soluble inmany of the more common inert normally liquid organic media, and whichare prepared by the reaction of monocarboxylic acids and/orpolycarboxylic acids, their anhydrides, their esters, or their halides,with a stoichiometric excess of a polyol such as the various diols,triols, etc.; illustrated previously, are highly preferred. Theaforesaid polyhydroxylcontaining esterification products willhereinafter be referred to as polyester polyols. Those polyester polyolswhich contain two alcoholic hydroxyl groups will hereinafter be termedpolyester diols. Illustrative of the polycarboxylic acids which can beemployed to prepare the polyester polyols preferably include thedicarboxylic acids, tricarboxylic acids, etc., such as maleic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, chlorendic acid, 1,2,4-butanetricarboxylicacid, phthalic acid, etc. This esterification reaction is welldocumented in the literature.

Higher functional alcohols suitable for reaction with the novelpolyisocyanates, e.g., the novel diisocyanates and the novelpolyisocyanate-containing polymers, include the triols such as glycerol,l,1,1-trimethylolpropane, 1,2,4-butanetriol, l,2,6-hexanetriol,triethanolamine, triisopropanolamine, and the like; the tetrols such aserythritol, pentaerythritol, N,N,N',N-tetrakis(Z-hydroxyethyl)ethylenediamine, =N, N,N,N tetrakis(2 hydroxypropyl) ethylenediamine,and the like; the pentols; the hexols such as dipentaerythritol,sorbitol, and the like; the alkyl glycosides such as the methylglucosides; the carbohydrates such as glucose, sucrose, starch,cellulose, and the like.

Other suitable hydroxyl-containing compounds include the monoand thepolyoxyalkylated derivaties of monoand polyfunctional compounds havingat least one reactive hydrogen atom. These functional compounds maycontain primary or secondary hydroxyls, phenolic hydroxyls, primary orsecondary amino groups, amide, hydrazino, guanido, ureido, mercapto,sulfino, sulfonamido, or carboxyl groups. They can be obtained byreacting, (1) monohydric compounds such as aliphatic and cycloaliphaticalcohols, e.g., alkanol, alkenol, methanol, ethanol, allyl alcohol,3-buten-l-ol, 2-e-thylhexanol, etc.; diols of the class HOtR-EOH andHO{-RORO-} H wherein R is alkylene of 2 to 4 carbon atoms and wherein nequals 1 to 10 such as ethylene glycol, propylene glycol, diethyleneglycol, dipropylene glycol, and the like; thiodiethanol; thexylenediols, 4,4-methylenediphenol, 4,4-isopropylidenediphenol,resorcinol; and the like; the mercapto alcohols such as mercaptoethanol;the dibasic acids such as maleic, succinic, glutaric, adipic, pimelic,sebacic, phthalic, tetrahydrophthalic, and hexahydrophthalic acids;phosphorous acids; phosphoric acids; the aliphatic, aromatic, andcycloaliphatic primary monoamines, like methylamine, ethylamine,propylamine, butylamine, aniline, and cyclohexylamine; the secondarydiamines like N,N-dimethylethylenediamine; and the amino alcoholscontaining a secondary amino group such as N-rnethylethanolamine; with(2) vicinal monoepoxides as exemplified by ethylene oxide,1,2-epoxypropane, 1,2-epoxybutane, 2,3- epoxybutane, isobutylene oxide,butadiene monoxide, allyl glycidyl ether, 1,2-epoxyoctene-7, styreneoxide, and mixtures thereof.

Further examples of polyols are the polyoxyalkylated derivatives ofpolyfunctional compounds having three or more reactive hydrogen atomssuch as, for example, the reaction products (adducts) of1,1,1-trimethylolpropane with a lower vicinal-epoxyalkane, e.g.,ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof,

in accordance with the reaction:

CHQOH CHaOHz-C-CHzOH CHz-CH2 CH2OH O CH2O-(CH2CH2O)XH wherein x-l-y-l-zequals 3 to 45, and more.

In addition to the polyoxyalkylated derivatives of l,l,1-trimethylolpropane, the following illustrative compounds are likewisesuitable: 1,1,1-trimethylolethane; glycerol; 1,2,4-butanetriol;l,2,6-hexanetriol; erythritol; pentaerythritol; sorbitol; the alkylglycosides such as the methyl glucosides; glucose; sucrose; the diaminesof the general formula H N(CH NH where n equals 2 to 12; 2-(methylamino)ethylamine; the various phenyleneand toluenediamines;benzidine; 3,3-dimethyl-4,4'-biphenyldiamine; 4,4-methylenedianiline;4,4',4"-methylidynetrianiline, the cycloaliphatic diamines such as2,4-cyclohex anediamine, and the like; the amino alcohols of the generalformula HO(CH NH where n equals 2 to 10; the polyalkylenepolyamines suchas diethylenetriamine, triethylenetetramine, tetraethylenepentamine, andthe like; the polycarboxylic acids such as citric acid, aconitic acid,

mellitic acid, pyromellitic acid, and the like; and polyfunctionalinorganic acids like phosphoric acid. The aforesaid polyfunctionalpolyoxyalkylated compounds will be referred to hereinafter aspolyoxyalkylated polyols. The polyoxyalkylated polyols which contain twoalcoholic hydroxyl groups will be termed polyoxyalkylated diols whereasthose which contain a sole alcoholic hydroxyl group will be referred toas polyoxyalkylated mono-ols.

Illustrative aminocontaining compounds which are contemplated are thosewhich contain at least one primary amino group (NH or secondary aminogroup (-NHR wherein R is hydrocarbyl such as alkyl, aryl, cycloalkyl,alkaryl, aralkyl, etc.), or mixtures of such groups. Preferredamino-containing compounds are those which contain at least two of theabove groups. Illustrative of the amino-containing compounds include thealiphatic amines such as the alkylamines, e.g., the methyl-, ethyl-,n-propyl-, isopropyl-, n-butyl-, sec-butyl-, isobutyl-, tert-butyl-,n-amyl-, n-hexyl-, and 2-ethylhexylamines, as well as the correspondingdialkylamines; the aromatic amines such as aniline, ortho-toluidine,meta-toluidine, and the like; the cycloaliphatic amines such ascyclohexylamine, dicyclohexylamine, and the like; the heterocyclicamines such as pyrrolidine, piperidine, morpholine, and the like; thevarious aliphatic diamines of the general formula H N(CH ),,NHmonosecondary diamines of the general formula R"NH(CR NH and disecondarydiamines of the general formula RNH(CH NHR", where n equals 2 to 10, andmore, and where R" is hydrocarbyl such as alkyl, aryl, aralkyl, alkaryl,or cycloalkyl; the etheric diamines of the formula Illustrative of thehigher functional amino-containing r compounds which can be employedinclude, for example, higher polyalkylenepolyamines such asdiethylenetriamine, triethylenetetramine, tetraethylenepentamine,dipropylenetriamine, tripopylenetetramine, tetrapropylenepentamine, andthe like; 1,2,5-benzenetriamine; toluene-2,4,6-triamine;4,4,4"-methylidynetrianiline; and the like; the polyamines obtained byinteraction of aromatic monoamines with formaldehyde or other aldehydes,for

example:

NH; IIIHZ 3 201120 Q I R Oom- NH2 R2 I NHz and other reaction productsof the above general type, where R is, for example, hydrogen or alkyl.

Illustrative of the carboxyl-containing compounds include those organiccompounds which contain at least one carboxyl group (COOH) asexemplified by the monocarboxyl-containing compounds such as alkanoicacids; the cycloalkanecarboxylic acids; the monoesterified dicarboxylicacids, e.g.,

wherein R is an organic radical such as oxahydrocarbyl, hydrocarbyl,etc., and R is the divalent residue of a dicarboxylic acid after removalof the two dicarboxylic groups; the polycarboxylic acids, e.g., thealiphatic, cycloaliphatic, and aromatic dicarboxylic acids; and thelike. Specific examples include propionic acid, butyric acid, valericacid, dodecanoic acid, acrylic acid, cyclohexanecarboxylic acid, themono-Z-ethylhexyl ester of adipic acid, succinic acid, maleic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, chlorendic acid, 4,4-oxydibutyric acid, 5,5'-oxydivalericacid, 6,6-oxydihexanoic acid, 4,4-thiodibutyric acid, 5,5'-thiodivalericacid, 6,6'-thiodihexanoic acid, itaconic acid, phthalic acid,isophthalic acid, terephthalic acid, the tetrachlorophthalic acids,1,5-naphthoic acid, 2,7-naphthoic acid, 2,6-naphthoic acid,3,3'-methylenedibenzoic acid, 4,4-(ethylenedioxy)dibenzoic acid,4,4-biphenyldicarboxylic acid, 4,4-sulfonyldibenzoic acid,4,4-oxydibenzoic acid, the various tetrahydrophthalic acids, the varioushexahydrophthalic acids, tricarballylic acid, aconitic acid, citricacid, hemimellitic acid, trimellitic acid, trimesic acid, pyromelliticacid, l,2,3,4-butanetetracarboxylic acid, and the like. Thepolycarboxyl-containing esterification products which range from liquidto noncrosslinked solids and which are prepared by the reaction ofpolycarboxylic acids, their anhydride, their esters, or their halides,with a stoichiometric deficiency of a polyol such as diols, triols,etc., can also be employed. These polycarboxyl-containing esterificationproducts will here inafter be referred to as polycarboxy polyesters.

Compounds which contain at leats two different groups of the class ofamino (primary or secondary), carboxyl, and hydroxyl, and preferablythose which contain at least one amino group and at least one hydroxylgroup, can be exemplified by the hydroxy-carboxylic acids, theaminocarboxylic acids, the amino alcohols, and the like. Illustrativeexamples include 2-hydroxypropionic acid, 6-hydroxycaproic acid,ll-hydroxyundecanoic acid, salicylic acid, para-hydroxybenzoic acid,beta alanine, 6- aminocaproic acid, 7-aminoheptanoic acid,ll-aminoundecanoic acid, para-aminobenzoic acid, and the like; the aminoalcohols of the general formula where n equals 2 to 10; otherhydroxyalkylamines such as N-methylethanolamine, isopropanolamine,N-mcthylisopropanolamine, and the like; the aromatic amino alcohols likepara-amino-phenethyl alcohol, para-aminoalpha-methylbenzyl alcohol, andthe like; the various cycloaliphatic amino alcohols such as4-aminocyclohexanol, and the like; the higher functional amino alcoholshaving a total of at least three hydroxy and primary or secondary aminogroups such as the dihydroxyalkylamines, e.g., diethanolamine,diisopropanol amine, and the like; 2 (2- amino ethylamino ethanol;2-amino-2- (hydroxymethyl 1,3-propanediol; and the like.

The initiated lactone polyesters which contain free hydroxyl group(s)and/or carboxyl group(s) represent extremely preferred active hydrogencontaining compounds. These initiated lactone polyesters are formed byreacting, at an elevated temperature, for example, at a temperature offrom about 50 C. to about 250 C., an admixture containing a lactone andan organic initiator; said lactone being in molar excess with relationto said initiator; said lactone having from six to eight carbon atoms inthe lactone ring and at least one hydrogen substituent on the carbonatom which is attached to the oxy group in said ring; said organicinitiator having at least one reactive hydrogen substituent preferablyof the group of hydroxyl, primary amino, secondary amino, carboxyl, andmixtures thereof, each of said reactive hydrogen substituents beingcapable of opening the lactone ring whereby said lactone is added tosaid initiator as a substantially linear group thereto; said initiatedlactone polyesters possessing, on the average, at least two of saidlinear groups, each of said linear groups having a terminal oxy group atone end, a carbonyl group at the other end, and an intermediate chain offrom five to seven carbon atoms which has at least one hydrogensubstituent on the carbon atom in said intermediate chain that isattached to said terminal oxy group. The aforesaid polyesters Willhereinafter be referred to, in the generic sense, as initiated lactonepolyesters which term will also include the various copolymers such aslactone copolyesters, lactone polyester/polycarbonates, lactonepolyester/ polyethers, lactone polyester/polyester/polycarbonates,lactone polyester/polyester, etc. These initiated lactone polyesterswill contain at least one hydroxy group and/ or at least one carboxylgroup depending, of course, on the initiator and reactants employed.Those initiated lactone polyesters which contain at least threealcoholic hydroxyl groups will be referred to as initiated lactonepolyester polyols; those with two alcoholic hydroxyl groups will betermed initiated lactone polyester diols. On the other hand, theinitiated lactone polyesters which contain at least two carboxyl groupswill be referred to as initiated polycarboxy lactone polyesters.

The preparation of the aforesaid hydroxyl-containing and/orcarboxyl-containing initiated lactone polyesters can be effected in theabsence or presence of an ester interchange catalyst to give initiatedlactone polyesters of widely varying and readily controllable molecularweights without forming water of condensation. These lactone polyestersso obtained are characterized by the presence of recurring linearlactone units, that is, carbonylalkyleneoxy wherein x is from 4 to 6,and wherein the R variables have the values set out in the nextparagraph.

The lactone used in the preparation of the initiated lactone polyestersmay be any lactone, or combination of lactones, having at least sixcarbon atoms, for example, from six to eight carbon atoms, in the ringand at least one hydrogen substituent on the carbon atom which isattached to the oxy group in said ring. In one aspect, the lactone usedas starting material can be represented by the general formula:

at irnonanc=o in which n is at least four, for example, from four tosix, at least n+2 Rs are hydrogen, and the remaining Rs are substituentsselected from the group consisting of hydrogen, alkyl, cycloalkyl,alkoxy and single ring aromatic hydrocarbon radicals. Lactones havinggreater number of substituents other than hydrogen on the ring, andlactones having four carbon atoms in the ring, are considered unsuitablebecause of the tendency that polymers thereof have to revert to themonomer, particularly at elevated temperature.

The lactones which are preferred in the preparation of thehydroxyl-containing and/or carboxyl-containing initiated lactonepolyesters are the epsilon-caprolactones having the general formula:

22 wherein at least six of the R variables are hydrogen and theremainder are hydrogen, alkyl, cycloalkyl, alkoxy, or single ringaromatic hydrocarbon radicals, none of the substituents contain morethan about twelve carbon atoms, and the total number of carbon atoms inthe substituents on the lactone ring does not exceed about twelve.

Among the substituted epsilon-caprolactones considered most suitable arethe various monoalkyl epsilon-caprolactones such as the monomethyl-,monoethyl-, monopropyl-, monoisopropyl-, etc. to monododecylepsilon-caprolactones; dialkyl epsilon-caprolactones in which the twoalkyl groups are substituted on the same or different carbon atoms, butnot both on the epsilon carbon atom; trialkyl epsilon-caprolactones inwhich two or three carbon atoms in the lactone ring are substituted, solong as the epsilon carbon atom is not disubstituted; alkoxyepsilon-caprolactones such as methoxy and ethoxy epsiloncaprolactones;and cycloalkyl, aryl, and aralkyl epsiloncaprolactones such ascyclohexyl, phenyl and benzyl epsilon-caprolactones.

Lactones having more than six carbon atoms in the ring, e.g.,zeta-enantholactone and eta-caprylolactone can be employed as startingmaterial. Mixtures comprising the C to C lactones illustratedpreviously, with/ without, for instance, the alpha,alpha-disubstituted-beta-propiolactone, e.g., alpha,alpha-dimethyl-beta-propiolactone, alpha,alpha-dichloromethyl-beta-propiolactone, etc.; with/ without, forinstance, oxirane compounds, e.g., ethylene oxide, propylene oxide,etc.; with/without, for instance, a cyclic carbonate, e.g.,4,4-dimethyl-2,6-dioxacyclohexanone, etc.; are also contemplated.

Among the organic initiators that can be employed to prepare theinitiated lactone polyesters include the carboxyl-containing,hydroxyl-containing, and/or amino-com taining compounds illustratedpreviously, e.g., those compounds which have at least one reactivehydrogen substituent as determined according to the Zerewitinoif method.

The initiator is belived to open the lactone ring to produce an ester oramide having one or more terminal groups that are capable of openingfurther lactone rings and thereby adding more and more lactone units tothe growing molecule. Thus, for example, the polymerization ofepsilon-caprolactone initiated With an amino alcohol is believed to takeplace primarily as follows:

wherein R (of the initiator and the resulting initiated lactonepolyester product) is an organic radical such as an aliphatic,cycloaliphatic, aromatic, or heterocyclic radical, and wherein a=b+c.

The reaction of a carboxyl-containing initiator withepsilon-caprolactone is believed to proceed as follows:

RCOOH a (IJI'IZCHZCI'I2OI'IZCZO It will be appreciated from thepreceding illustrative equations that where a plurality of lactone unitsare linked together, such linkage is effected by monovalently bondingthe oxy (O) moiety of one unit to the carbonyl 23 moiety of an adjacentunit. The terminal lactone unit will have a terminal hydroxyl orcarboxyl end group depending, of course, on the initiator employed.

The preparation of the initiated lactone polyester can be carried out inthe absence of a catalyst though it is preferred to effect the reactionin the presence of an ester exchange catalyst. The organic titaniumcompounds that are especially suitable as catalysts include thetetraalkyl titanates such as tetraisopropyl titanate and tetrabutyltitanate. Additional preferred catalysts include, by way of furtherexamples, the stannous diacylates and stannic tetraacylates such asstannous dioctanoate and stannic tetraoctanoate. The tin compounds, theorganic salts of lead and the organic salts of manganese which aredescribed in U.S. 2,890,208 as well as the metal chelates and metalacylates disclosed in U.S. 2,878,236 also represent further desirablecatalysts which can be employed. The disclosures of the aforesaidpatents are incorporated by reference into this specification.

The catalysts are employed in catalytically significant concentration.In general, a catalyst concentration in the range of from about 0.0001and lower, to about 3, and higher, weight percent, based on the weightof total monomeric feed, is suitable. The lactone polymerizationreaction is conducted at an elevated temperature. In general, atemperature in the range of from about 50 C., and lower, to about 250 C.is suitable; a range from about 100 C. to about 200 C. is preferred. Thereaction time can vary from several minutes to several days dependingupon the variables illustrated immediately above. By employing acatalyst, especially the more preferred catalysts, a feasible reactionperiod would be about a few minutes to about hours, and longer.

The polymerization reaction preferably is initiated in the liquid phase.It is desirable to effect the polymerization reaction under an inertatmosphere, e.g., nitrogen.

The preparation of the lactone polyesters via the preceding illustrativemethods has the advantage of permitting accurate control over theaverage molecular weight of the lactone polyester products and furtherof promoting the formation of a substantially homogeneous lactonepolyester in which the molecular weights of the individual molecules arereasonably close to the average molecular weight, that is, a narrowmolecular weight distribution is obtained. This control is accomplishedby preselecting the molar proportions of lactone and initiator in amanner that will readily be appreciated by those skilled in the art.Thus, for example, if it is desired to form a lactone polyester in whichthe average molecular weight is approximately fifteen times themolecular weight of the initial lactone, the molar proportions oflactone and initiators utilized in the polymerization reaction are fixedat approximately :1 inasmuch as it is to be expected that on the averagethere will be added to each molecule of initiator approximately fifteenlactone molecules.

The initiated lactone polyesters which are contemplated have averagemolecular Weights as low as 300 to as high as about 7000, and evenhigher still to about 9000. With vinyl polymers containing a pluralityof active hydrogen substituents, e.g., hydroxyl, amino, etc., asinitiators, the average molecular weight of the initiated lactonepolyesters can easily go as high as 14,000, and higher. Generally,however, the average molecular weight of the initiated lactone polyesteris from about 300 to about 9000, preferably from 600 to about 5000.

As intimated previously, also within the term and the scope of theinitiated lactone polyesters are those in which the linear lactone unitsneed not necessarily be connected directly to one another. This isreadily accomplished, for example, by reacting lactone(s) withcombinations of initiators such as dibasic acid(s) plus glycols(s),diamine(s), or amino alcohol(s) such as those exemplified previously.This reaction can be effected at an elevated temperature, e.g., about100 C. to about 200 C., with all the reactants present, or the reactionof the dibasic acid 24 with the glycol, diamine, or amino alcohol can beaccomplished first, and then the resulting amino-, hydroxyl-, orcarboxyl-containing products (depending on the reactants and theconcentration of same) can be reacted with the lactone to yieldhydroxyl-terminated and/or carboxylterminated initiated lactonepolyesters. Moreover, as also indicated previously, the term and thescope of the hydroxyland/ or carboxyl-containing initiated lactonepolyesters include the "oxyalkylene-carboxy-alkylenes" such as describedin U.S. Pat. No. 2,962,524 which are incorporated by reference into thisdisclosure. In addition the term and scope of the hydroxyl-containinginitiated lactone polyesters also includes the reaction of an admixturecomprising a C -C lactone(s), a cyclic carbonate( s), and an initiatorhaving at least one group, preferably at least two groups, of the classof hydroxyl, primary amino, or secondary amino, or mixtures thereof,under the operative conditions discussed above. Exemplary cycliccarbonates include 4,4-dimethyl-2,6-dioxacyclohexanone, 4,4-dichloromethyl 2,6 dioxacyclohexanone, 4,4dicyanomethyl-2,6-dioxacyclohexanone, 4,4 diethyl 2,6dioxacyclohexanone, 4,4 dimethoxymethyl 2,6 dioxacyclohexanone; and thelike. Consequently, where a mixture of linear lactone units, i.e.,

units which are properly termed carbonylalkyleneoxy) and linearcarbonate units (i.e.,

units which can be termed carbonyloxyalkyleneoxy) are contained in thepolymer chain or backbone, the carbonyl moiety of one linear unit willbe monovalently bonded to the oxy moiety of a second linear unit. Theoxy moiety of a terminal linear unit will be bonded to a hydrogensubstituent to thus form a hydroxyl end group. Moreover, the point ofattachment of the initiator and a linear unit (lactone or carbonate)will be between the carbonyl moiety of said unit and the functionalgroup (hydroxyl or amino) of said initiator sans the active hydrogensubstituent of said group.

The preferred initiated lactone polyesters include those Which containat least about 50 mol percent of carbonylpentamethyleneoxy units thereinand which possess an average molecular weight of from about 500 to about5000, particularly from about 600* to about 4000. The remaining portionof the molecule can be comprised of in addition to the initiator,essentially linear units derived from a cyclic carbonate especiallythose illustrated previously; an oxirane compound especially ethyleneoxide, propylene oxide, and/or butylene oxide; a monoand/ orpolyalkyl-substituted epsilon-caprolactone especially the monoand/orpolymethyl and/or ethyl-substituted epsilon-caprolactones; and/or analpha, alphadisubstituted-beta-propiolactone especially thoseexemplified previously. The so-called initiated lactone homopolyestersderived from reacting epsilon-caprolactone with an initiator arelikewise included within the preferred lactone polyesters. The initiatedlactone polyester polyols, and in particular, the substantially linearinitiated lactone polyester diols, are exceptionally preferred.

If desired, various compounds can be employed as catalysts in theisocyanato/active hydrogen reactions. Compounds which are oftentimesuseful in catalyzing said isocyanato-active hydrogen reactions includethe tertiary amines, phosphines, and various organic metallic compoundsin which the metal can be bonded to carbon and/ or other atoms such asoxygen, sulfur, nitrogen, halo, hydrogen, and phosphorus. The metalmoiety of the organic metallic compounds can be, among others, tin,titanium, lead, potassium, sodium, arsenic, antimony, bismuth,manganese, iron, cobalt, nickel, and zinc. Of those which deservespecial mention are the organic metallic compounds which contain atleast one oxygen to metal bond and/ or at least one carbon to metalbond, especially wherein the metal moiety is tin, lead, bismuth,arsenic, or antimony. The tertiary amines, the organic tin compounds(which includes the organotin compounds), and the organic lead compoundsare eminently preferred. Preferred subclasses of organic metalliccompounds include the acylate, particularly the alkanoates, andalkoxides of Sn(II), Sn(IV), Pb(II), Ti(IV), Zn(IV), C(II), Mn(II),Fe(III), Ni(II), K, and Na. An additional subclass which is extremelyuseful is the dialkyltin, dialkanoates.

Inorganic metallic compounds such as the hydroxides, oxides, halides,and carbonates of metals such as the alkali metals, the alkaline earthmetals, iron, zinc, and tin are also suitable.

Specific catalysts include, by way of illustrations, 1,4-diazabicyclo[2.2.2]octane, N,N,N',N tetramethyl-1,3- butanediamine,bis[2 (N,N-dimethylamino)ethyl] ether, bis[2 N,N dimethylamino 1methylethyl] ether, N- methylmorpholine, sodium acetate, potassiumlaui'ate, stannous octanoate, stannous oleoate, lead octanoate,tetrabutyl titanate, ferric acetylacetonate, cobalt naphthenate,tetramethyltin, tributyltin chloride, tributyltin hydride, trimethyltinhydroxide, dibutyltin oxide, dibutyltin dioctanoate, dibutyltindilaurate, butyltin trichloride, triethylstibine oxide, potassiumhydroxide, sodium carbonate, magnesium oxide, stannous chloride, stannicchloride, bismuth nitrate. Other catalysts include those set forth inPart IV Kinetics and Catalysis of Reactions of Saunders et al.Polyurethanes: Chemistry and Tech nologyPart I. Chemistry, IntersciencePublishers, which is incorporated by reference into this disclosure. Inmany instances, it is particularly preferred to employ combinations ofcatalysts such as, for example, a tertiary amine plus an organic tincompound.

The isocyanato-reactive hydrogen reactions can be conducted over a widetemperature range. In general, a temperature range of from about 0 toabout 250 C. can be employed. To a significant degree, the choice of thereactants and catalyst, if any, influences the reaction temperature. Ofcourse, sterically hindered novel diisocyanates or active hydrogencompounds will retard or inhibit the reaction. Thus, for example, thereaction involving isocyanato with primary amino or secondary amino canbe effected from about 0 C. to about 250 C. whereas theisocyanato-phenolic hydroxyl reaction is more suitable conducted fromabout 30 C. to about 150 C. Reactions involving primary alcoholichydroxyl, secondary alcoholic hydroxyl, or carboxyl with isocyanato areeffectively conducted from about 20 C. to about 250 C. The upper limitof the reaction temperature is selected on the basis of the thermalstability of the reaction products and of the reactants whereas thelower limit is influenced, to a significant degree, by the rate ofreaction.

The time of reaction may vary from a few minutes to several days, andlonger, depending upon the reaction temperature, the identity of theparticular active hydrogen compound and diisocyanate as well as upon theab sence or presence of an accelerator or retarder and the identitythereof, and other factors. In general the reaction is conducted for aperiod of time which is at least sufficient to provide the addition orattachment of the active hydrogen from the active hydrogen compound tothe isocyanato nitrogen of the novel diisocyanate. The remainder of theactive hydrogen compound becomes bonded to the carbonyl carbon unlessdecarboxylation or further reaction occurs. The following equationillustrates the reaction involved.

t? RN=C=O H-Z RNI-I-CZ wherein H-Z represents the active hydrogencompound. Thus, by way of illustrations the reaction of isocyanato (NCO)with (a) hydroxyl (OH) results in the l? NHCO-- group; (b) primary amino(-NH results in the NH( JNH group; (c) secondary amino (NHR) results inthe Nn( iNR group; (d) thiol (SH) results in the o NH S- group; (e)carboxyl (COOH) can be considered to result in the intermediate 0 [-NHi30i 3-] which decarboxylates to the 0 NHiigroup; (f) ureylene (NH NH-firesults in the o H N l' 1-'1 O=CNH group (biuret); (g) amido (-i )NHR)results in the CNCNII- t l t group (carbonylurea); (h) urethane (NHC iiresults in the o=oNH group (allophanate); (i) water (HOH) can beconsidered to result in the intermediate which decarboxylates to the NHgroup; and the like. Most desirably, conditions are adjusted so as toachieve a practical and commercially acceptable reaction rate depending,to a significant degree, on the end use application which iscontemplated. In many instances, a reaction period of less than a fewhours is oftentimes sufficient for the intended use.

The isocyanato-reactive hydrogen reactions, in many instances, arepreferably accomplished in the presence of a catalytically significantquantity of one or more of the catalysts illustrated previously. Ingeneral, a catalyst concentration in the range of from about 0.001weight percent, and lower, to about 2 weight percent, and higher, basedon the total weight of the reactants, has been observed to be useful.

The concentration of the reactants can be varied over a wide range.Thus, for example, one can employ the active hydrogen compound in suchrelative amounts that there is provided as low as about 0.1 equivalent(group) of active hydrogen, and lower, per equivalent (group) ofisocyanato. In general, about 0.2 and oftentimes about 0.25 equivalentof active hydrogen represent more suitable lower limits. The upper limitcan be as high as about 7 equivalents of active hydrogen, and higher,per equivalent of isocyanato. However, for many applications, adesirable upper limit is about 3.5 equivalents of active hydrogen perequivalent of isocyanato. When employing bifunctional compounds (thosewhich contain two active hydrogen substituents such as hydroxyl,carboxyl, primary amino, secondary amino, etc.), a suitableconcentration would be from about 0.25 to about 3 equivalents of activehydrogen substituent from the bifunctional compound perequivalent ofisocyanato from the isocyanate. It is readily apparent that dependingupon the choice and functionality of the active hydrogen compound(s),the choice of the polyisocyanate(s), the proportions of the reactants,etc., there can be obtained a myriad of novel compounds and productswhich range from the liquid state to solids which can be fusible solids,thermoplastic solids, partially cured to essentially completely cured,thermoset solids, etc. The novel liquid to non-crosslinked solidcompositions contain a plurality of polymerizable ethylenic bonds whichserve as vinyl polymerization sites with vinyl monomers such as thoseillustrated previously, e.g., styrene, butadiene, vinyl chloride, etc.,under the operative conditions noted supra.

A class of novel compounds which deserve special mention are those whichcontain the grouping therein. These compounds are characterized asfollows:

II H z CNHROCIMCORNIICZ wherein R and R have the values set out inFormula I supra, and wherein Z is an abbreviated form for themonofunctional active organic compound sans the active hydrogen atoms.Illustrative Z radicals include those which result from the reaction of,for example, stoichiometric quantities of the novel diisocyanates ofFormula I supra with monofunctional active organic compounds asillustrated by primary amines, secondary amines, primary alcohols,secondary alcohols, phenols, primary thiols, secondary thiols, imines,amides, ureas, etc. The scope of Z is readily apparent from thedescription re the active hydrogen compounds as well as from aconsideration of Equation X supra. Moreover, by reacting equimolaramounts of the diisocyanates of Formula I with the aforeillustratedmonofunctional active organic compounds, there can be obtainedmonoisocyanates of the formula:

XIA

ll ll ooNRot lRicoRNficz A further class of polymeric products whichdeserve to be highlighted are those novel polymers which arecharacterized by Unit XII below:

wherein R", R, R, and m have the values (including the provisos) set outin Unit IX supra, and wherein Z is adequately described in thediscussion re Formula XI supra.

wherein R", R, R, R in and x have the meanings set out in Unit lXA andwherein Z has the value set out in Unit XI supra.

Highly desirable subclasses of novel polymeric products are those whichare characterized by the following Units (XIIB, XIIC, XIID) below:

XIIB

(IV- 910 RNHPJZ wherein the variables R, R R, m, and x have the valuesnoted in Unit IXA supra;

XIIC o o ("3o RNHPJZ -(|1HCH ('30 ENE 02 l) l,

wherein R is an alkylene radical which from 2 to 12 carbon atoms;

XIID

preferably contains o o RNH O z wherein R has the broad and preferredvalues set out in Unit IXC supra, and wherein R and x have the valuesnoted in Unit IXA supra. The variable Z in the aforesaid Units isdescribed in Unit XI supra.

The novel polymeric products contain at least one of the unitsdesignated as Units XII through XIID, and in general, these productscontain a plurality of said units, e.g., upwards to 200, and more.

A useful subarea of polymeric products result from the reaction of thenovel telomers of the bis[omega-isocyanato-(C C alkyl)] fumarates, thecitraconates, and the itaconates, with a monofunctional active organiccompound such as those illustrated previously. Those relative lowmolecular weight polymeric products characterized by at least two andupwards to about 20, preferably 3 to about 10, of the units set forthbelow are suitable for many useful applications:

'- (HEOUHCILNHICIJ Z] It is pointed out that the proviso noted inFormula I applies to Units lX through IXF, Formulas XI and XIA, andUnits XII through XIlF. It is also pointed out that the novel polymericproducts which are characterized by one or more of Units XII throughXIIF therein can also contain one or more of the units designated asUnits IX through IXF therein. Both types of units can occur, e.g. UnitIX and XII, in the novel polymeric products via the vinyl polymerizationof an admixture comprising a diisocyanate of Formula I, a blockedisocyanate of Formula XI with/without an ethylenically unsaturatedorganic compound. In addition, useful and interesting polymeric productsare obtained by the vinyl polymerization of an admixture comprising thepartially blocked isocyanate of Formula XIA with/without thediisocyanate of Formula I, with/without the blocked isocyanate ofFormula XI, and with/ without an ethylenically unsaturated organiccompound.

A particular desirable class of novel polyurethane diols which arecontemplated within the scope of the teachings of this specification arethose which result from the reaction of a dihydroxy compound such asthose illustrated previously, with a molar deficiency, i.e., astoichiometric deficiency, of the novel diisocyanates which fall withinFormula I supra. The highly preferred dihydroxy compounds are thealkylene glycols, the polyether glycols, the polyoxyalkylated diols, thepolyester diols, and the initiated lactone polyester diols, especiallythose dihydroxycompounds which have average molecular weights as low asabout 60 and as high as about 7000-, and higher. A preferred averagemolecular weight range is from about 300 to about 5000. The initiatedlactone polyester diols which have an average molecular weight of fromabout 600 to about 4000 are eminently preferred since within thismolecular weight range there can be prepared, for example, polyurethaneproducts such as cast resins, thermoplastic products, and elastic fiberswhich exhibit outstanding performance characteristics. Equation XIIIbelow illustrates the linear extension reaction involved:

II II HO [A O CNHQNHO O]nA OH Polyurehane Diol wherein HOA-OI-I is anabbreviated representation of the organic dihydroxy compounds, thevariable A being an organic divalent aliphatic radical such as thoseillustrated previously; wherein Q( NOO) is an abbreviated representationfor the novel diisocyanates encompassed within the scope of Formula Isupra, the variable Q representing the divalent unit if i R 0 c1110 0 R-the R and R variables of said unit having the assigned values of Formula'I supra; and wherein n is a number having an average value of at leastone.

It will be noted from Equation XIII that the degree of linear extensionis realistically controlled by the amount of. the reactants employed. Ifthe proportions of diol and diisocyanate are chosen so that the numberof reactive hydroxyl groups on the diol are equal to the number ofreactive isocyanate groups on the diisocyanate, then relatively long,high molecular weight chains can be formed. In general, one can employsuch relative amounts so that there is provided slightly greater thanone equivalent of hydroxyl group from the diol per equivalent ofisocyanato group from the diisocyanate. It is desirable, however, toemploy amounts of diol and organic diisocyanate (in Equation XIII sothat there is provided a ratio of from about 1.1 to about 2.2equivalents, and higher, of hydroxyl group per equivalent of isocyanatogroup, and preferably from about 1.3 to about 2 equivalents of hydroxylgroup per equivalent of isocyanato group.

It is to be understood that in lieu of the dihydroxy com pounds employedin Equation XIII one can employ higher functional polyols such as thetriols, tetrols, etc., and

obtain novel polyurethane triols, tetrols, etc. In addition, admixturesof dihydroxy compounds, or dihydroxy compounds plus higher functionalhydroxy compounds, can be empolyed.

An eminently preferred class of novel polyurethane diisocyanates whichare contemplated are those which result from the reaction of a dihydroxycompound exemplified previously, with a molar excess of the noveldiisocyanates of Formula I supra. The highly preferred dihydroxycompounds which can be employed include those illustrated in thediscussion re Equation XIII supra as well as the resulting polyurethanediol products of Equation XIII. Equation XIV below illustrates thislinear extension reaction involved:

XIV

HOAOH excess Q(NCO)2 wherein all the variables of Equation XIV have themeanings set out in Equation XIII previously.

It will be noted from Equation XIV that the use of an excess ofdiisocyanate provides an efiicient means of control over the degree oflinear extension of the polyurethane molecule. If the proportions ofdiol and diisocyanate are chosen so that the number of reactive terminalhydroxyl groups on the diol are equal to the number of reactiveisocyanate groups on the diisocyanate as indicated previously,relatively long, high molecular Weight chains would be formed. It isdesirable, for many applications, to employ amounts of diisocyanate anddiol in Equation XIV so that there is provided a ratio of greater thanabout one equivalent of diisocyanate per equivalent of diol, preferablyfrom about 1.05 to about 7 equivalents, and higher, of diisocyanate perequivalent of diol, and preferably still from about 1.2 to about 4equivalents of diisocyanate per equivalent of diol.

During and after preparation of the isocyanato-terminated reactionproducts it is oftentimes desirable to stabilize said reaction productsby the addition of retarders to slow down subsequent furtherpolymerization or less desirable side-reactions such as, for example,allophanate formation. Retarders may be added to the diisocyanate, diol,and/or the aforesaid reaction products. Illustrative of the retarderssuitable for the diol-diisocyanate reaction are hydrochloric acid,sulfuric acid, phosphoric acid, boric acid, acetyl chloride,para-toluenesulfonyl chloride, phosphorous trichloride, phosphorousoxychloride, sul furyl chloride, thionyl chloride, and sulfur dioxide.

In lieu of, or in conjunction With the dihydroxy reactants of EquationXIV, it is oftentimes desirable to employ higher functional polyols suchas the triols, tetrols, etc., and obtain novel polyurethanetriisocyanates, tetraisocyanates, etc.

Another particular desirable class of novel compounds which arecontemplated are the novel polyurea diamines which are prepared via thereaction of a diamino compound (which contain two groups from the classof primary amino, secondary amino, and mixtures thereof) as illustratedpreviously with a molar deficiency of the novel diisocyanates. EquationXV below illustrates this linear extension reaction involved:

XV HIII-D-ITIH deficient Q(N CO)2 t t t l HIYIDIFICNHQ,NHClTIDI;IH R L RR L R Polyurea Diamine wherein HNDII\ H R R is an abbreviatedrepresentation of a diamine compound (the R variables representinghydrogen; a monovalent hydrocarbon or azahydrocarbon radical, e.g.,alkyl, aryl, aralkyl, azalkyl, and the like; and D representing adivalent organic radical, e.g., a divalent aliphatic, alicyclic,aromatic, or heterocyclic radical), and wherein Q(NCO) and n have themeanings set forth in Equation XIII supra. In general, one can employslightly greater than about one and upwards to about two, and higher,equivalents of amino group per equivalent of isocyanato group. In lieuof, or in conjunction with, the diamino reactants of Equation XV, it isoftentimes desirable to employ higher functional polyamines such as thetriamines, tetraamines, etc., and obtain novel polyurea triamines,polyurea tetraamines, etc.

On the other hand, the use of a molar excess of diisocyanate withrelation to the diamino compound produces novel polyurea diisocyanatesas illustrated by Equation XVI:

XVI HNDNH excess Q(NCO)2-1 Lttl.

Polyurca Diisocyanate In the reaction exemplified by Equation XVI supra,there can be employed slightly greater than about one and upwards toabout 3, and higher, equivalents of isocyanato group per equivalent ofamino group. Higher functional polyamines can be employed instead of, oradmixed with, the diamines, to thus yield novel polyurea triisocyanates,polyurea tetraisocyanates, etc.

If desired, the preceding novel linear extension reactions can becarried out in the presence of essentially inert normally-liquid organicvehicles such as various organic solvents, depending upon the furtherapplication which may be intended for said reaction products.

In another aspect, the invention is directed to the preparation of castpolyurethane systems. Highly useful rigid to flexible, polyurethaneresins which can range from slightly crosslinked products to highlycrosslinked products can be prepared by the novel diisocyanates ofFormula I supra and/or the novel polyisocyanate-containing polymersexemplified by Units IX to IXF supra and/or the polyurethanepolyisocyanato reaction products discussed in the section re EquationXIV with a polyfunctional chain extender which contains at least twofunctional groups that are primary amino (NH secondary amino (NI-IR),hydroxyl (OH), or mixtures thereof. The polyisocyanate andpolyfunctional chain extender are employed in such relative amounts thatthere is provided at least about one equivalent (group) of isocyanato(NCO) from the polyisocyanate per equivalent (group) of functional group(hydroxyl and/or amino) from the polyfunctional compounds. Whenemploying solely difunctional compounds as the chain extender(s), it isdesirable to employ such relative amounts that result in greater thanabout one equivalent of NCO, e.g., at least about 1.02 equivalents ofNCO, from the polyisocyanate per functional group from the difunctionalcompound. However, it is oftentimes highly satisfactory when employingpolyfunctional chain extenders which contain 3 or more functionalgroups, alone or in admixture with difunctional chain extenders, toemploy such relative amounts so that there is provided at least aboutone equivalent of --NCO from the polyisocyanate per equivalent offunctional group from the chain extender(s). Cast polyurethane resinshaving special utility as printing ink rollers, cast solid urethaneindustrial tires, mechanical goods such as seals, O-rings, gears, etc.,ladies shoe heels, and the like, can be prepared from castableformulations which provide from about 1.02 to about 1.6 equivalents ofNCO from the polyisocyanate per equivalent of functional group from thepolyfunctional chain extender. Optimum properties result from the highlypreferred castable formulations which provide from about 1.05 to about1.4 equivalents of NCO per equivalent of functional group.

It is further highly desirable that the aforesaid polyisocyanate be aprepolymer as defined in Equation XIV supra which has an averagemolecular weight of at least about 550 in the preparation of castpolyurethane resins. The upper limit can be as high as 8000 and higher.For many applications, a practical molecular Weight range is from about750 to about 5000. It is observed that Within the aforesaid molecularWeight limits there can be produced cast polyurethane resins which varyfrom extremely soft flexible products to relatively hard plasticproducts. Prepolymers which result from the reaction of diisocyanate andthe initiated lactone polyester polyols are eminently suitable sincecast resins Which possess high performaance characteristics can beobtained.

Among the polyfunctional chain extenders which can be employed in thecastable formulations are those organic compounds exemplified previouslywhich have two or more hydroxyl or amino (primary and secondary) groupsincluding mixtures of such groups such as the polyols (diols, triols,tetrols, etc.), the polyamines (diamines, triamines, etc.), aminoalcohols, and the like. Among the polyfunctional chain extenders Whichdeserve special mention because they result in especially useful castpolyurethane resins of high strength, high tear resistance, relativelylow permanent set, good solvent resistance, and/ or excellent abrasionresistance can be listed the following: 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, quinitol, 1,4 bis(2 hydroxyethoxy)benzene,4,4-bis[(2-hydroxyethoxy)phenyl]isopropylidene, trimethylolpropane,triisopropanolamine, ethanolamine, p-aminophenylethyl alcohol, 2,4- and2,6-toluenediamines, 3,3-dichloro-4,4'-diphenylenediamine, and 4,4methylene bis(o chloroaniline).

The preparation of the cast polyurethane products can take place over awide temperature range, e.g., from about room temperature to about 200C., and higher. The preferred temperature is in the range of from about50 C. to about 150 C. A highly preferred temperature range is from about60 C. to about C. The upper limit of the reaction temperature, asindicated previously, is realistically controlled by the thermalstability of the reactants and reaction products whereas the lower limitis regulated, to a significant degree, by the reaction rate.

A valuable modification of the cast polyurethane aspect is the use of anadmixture containing the polyols exemplified previously with/without thenovel polyurethane diols (of Equation XIII) plus the novel diisocyanates(of Formula I) instead of, or in conjunction with, the prepolymer (ofEquation XIV). It is preferred that the previously exemplified polyolsbe substantially linear hydroxyl-terminated polymers. It is highlypreferred that these polymers have an average molecular weight of atleast about 60 and upwards to 6000, and higher, and preferably fromabout 300 to about 5000. The hydroxylterminated polymers which areeminently suitable include the alkylene glycols, the polyether glycols,the polyester diols. the polyoxyalkylated diols, and the initiatedlactone polyester diols. In this modification, the ratios of theequivalents of NCO and the equivalents of functional groups are the sameas set forth above. It is understood, of course, that these ratios willinclude all the NCO groups and all the functional groups in the castableformulation regardless of the source. Thus, for example, if theformulation comprises novel polyurethane diol, novel diisocyanate, andalkanediol, one must take into consideration when computing theequivalents ratio of said formulation, the equivalents of NCO from thediisocyanate with relation to the sum of the equivalents of the hydroxylgroups from the polyurethane diol plus alkanediol.

A further desirable modification of the cast polyurethane aspect isdirected to the partial or incomplete reaction of the cast formulationto thus produce a thermoplastic reaction product mass which containsunreacted or free isocyanato groups. The aforesaid thermoplastic mass isrelatively stable or non-reactive at room temperature, e.g., about 20C., but possesses the characteristic of being further cured as, forexample, by curing same at an elevated temperature for a sufficientperiod of time. This curable, isocyanato-containing mass can be preparedby heating the cast formulation or system, e.g., to about 100 C., andhigher, and thereafter quenching the resulting partial reaction products(which contain a minor proportion of unreacted isocyanato groups) withan inert fluid in which said reaction products are insoluble, e.g., aninert normally liquid organic non-solvent. The aforesaid curable,isocyanato-containing thermoplastic mass can be stored for relativelylong periods of time or shipped to customers over great distanceswithout undergoing any appreciable reaction at ambient conditions, e.g.,about 20 C.

An extremely significant aspect is directed to the preparation ofthermoplastic polyurethane resins including curable polyurethanesystems. Such useful systems and/or resins can be prepared fromformulations (which include the reactants, especially the difunctionalreactants, reaction conditions, and modifications thereof) as set out inthe preceding aspect (re the cast polyurethanes) with the exception thatthere is employed at least about one equivalent of functional group,e.g., hydroxyl, primary amino, secondary amino, or mixtures thereof,from the polyfunctional chain extender per equivalent of isocyanato(-NCO) from the isocyanate source. In general, a practical upper limitwould be about 1.5 equivalents of functional group per equivalent ofNCO. Preferred formulations contain from about 1.02 to about 1.3equivalents of functional group per equivalent of NCO, preferably stillfrom about 1.05 to about 1.15 equivalents of functional group perequivalent of NCO. In other modifications, it is eminently preferredthat the thermoplastic formulation contain about one equivalent offunctional group per equivalent of isocyanato, especially to preparethermoplastic elastomers which exhibit high performance characteristics.

The thermoplastic and curable polyurethane resins can he cured orcrosslinked with an organic polyisocyanate. In this respect the noveldiisocyanates of Formula I supra, the novel polyisocyanato-containingpolymers exemplified previously, and/or polyisocyanates well known inthe literature can be employed, e.g., publication by Siefken [Annalen,562, pages 122-135 (1949)]. Polyisocyanates such as those produced bythe phosgenation of the reaction products of aniline and formaldehyde,or p,p',p-triphenylmethane triisocyanate, represent furtherillustrations.

In general, the cure can be effected by using an amount ofpolyisocyanate which is in stoichiometric excess necessary to react withany free or unreacted functional group from the polyfunctional chainextender. In general, from about 1 to about parts by 'weight ofadditional polyisocyanate per 100 parts by weight of curablepolyurethane resin is adequate to accomplish the cure for mostapplications. A preferred range is from about 2.5 to about 6 parts byweight of polyisocyanate per 100 parts by weight of curable stock. Theadditional polyisocyanate can be admixed with the curable polyurethanestock on a conventional rubber mill or in any suitable mixing device andthe resulting admixture is cured in the mold at an elevated temperature,e.g., from about 125-l60 C., in a relatively short period, e.g., a fewminutes, or longer. In the mold, the cure is accomplished apparently bya reaction of excess amino or hydroxyl groups with the newly admixedpolyisocyanate, and secondly by reaction of the remaining free terminalisocyanate groups with hydrogen atoms of the urea and urethane groups toform a crosslinked resin. By this procedure, there can be obtained curedpolyurethane products which range from highly elastomeric materials 34possessing excellent tensile strength and exceptional low brittletemperature to tough, rigid rubbery materials.

Various modifying agents can be added to the castable or curableformulations among which can be listed fillers such as carbon blacks,various clays, zinc oxide, titanium dioxide, and the like; various dyes;plasticizers such as polyesters which do not contain any reactiveend-groups, organic esters of stearic and other fatty acid, metal saltsof fatty acids, dioctyl phthalate tetrabutylthiodisuccinate; glass;asbestos; and the like.

A modification of the thermoplastic and curable polyurethane resins isthe preparation of formulations using diisocyanates 'which are wellknown in the literature, and subsequently effecting the cure with thenovel polyisocyanates of Formulas I or XIV or thepolyisocyanatecontaining polymers characterized by units IX to IXFsupra.

A particularly preferred aspect is directed to the preparation ofelastomeric products, especially elastomeric films and elastic fibers.It has been discovered quite surprising, indeed, that there can beprepared exceptional elastic polyurethane films and fibers which arederived from substantially linear hydroxyl terminated polymers having anaverage molecular weight greater than about 500 and the noveldiisocyanates of Formula I supra. The elastic films and fibers of thisaspect are characterized by outstanding resistance to sunlightdegradation, outstanding elongation, high resistance to fume aging,i.e., resistance to breakdown caused by nitrous oxide which is commonlyfound as an impurity in the atmosphere, high tensile and modulusproperties, and/or good stability to oxidizing agents such as chlorinebleach.

These novel elastomeric films and fibers can be prepared by firstreacting the aforesaid substantially linear hydroxyl-terminated polymerwith a molar excess of the novel diisocyanate (of Formula I) to producea substantially linear isocyanato-terminated polyurethane product (knownas a prepolymer). The chain extension reaction of said prepolymer with abifunctional curing compound in accordance with, for instance, wellknown cast or spinning techniques results in elastomeric films or fibersas may be the case. In a useful embodiment, the aforesaid substantiallylinear hydroxyl-terminated polymers can be linearly extended by reactionwith a molar deficiency of an organic diisocyanate to yieldsubstantially linear hydroxyl-terminated polyurethane products whichproducts then can be reacted with a molar excess of the noveldiisocyanates to obtain the prepolymer.

The substantially linear hydroxyl-terminated polymer possesses anaverage molecular Weight of at least about 500, more suitably at leastabout 700, and preferably at least about 1500. The upper averagemolecular weight can be as high as 5000, and higher, a more suitableupper limit being about 4000. For many of the novel elastic fibers andfilms which exhibited a myriad of excellent characteristics, the averagemolecular weight of the starting hydroxyl terminal polymer did notexceed about 3800.

In addition, the hydroxyl-terminated polymers possess a hydroxyl numberbelow about 170, for example, from about 20 to about and a melting pointbelow about 70 C., and preferably below about 50 C.

Exemplary of the substantially linear hydroxyl-terminated polymers whichare contemplated include the alkylene glycols, the polyether glycols,the polyoxyalkylated diols, the polyester diols, and the initiatedlactone polyester diols. The initiated lactone polyester diols areeminently preferred since elastomeric films and elastic fibersexhibiting outstanding performance characteristics can be obtained. Ofthe highly preferred initiated lactone polyester diols are includedthose which are characterized by at least about 50 mol percent ofcarbonylpentamethyleneoxy units therein and which possess an averagemolecular weight of from about 500 to about 5000, particularly fromabout 600 to about 4000. The remaining portion of the molecule can becomprised of, in addition to the initiator, essentially linear unitsderived from a cyclic carbonate such as those illustrated previously,e.g., 4,4-dimethyl-2,6-dioxacyclohexanone, 4,4 dicyanomethyl 2,6dioxacylohexanone, 4 ,4 -dich1oromethyl 2,6 dioxacyclohexanone, 4,4-di(methoxymethyl) 2,6 dioxacyclohexanone, and the like; an oxiranecompound especially ethylene oxide, 1,2- epoxypropane, the epoxybutanes,etc.; a mono-, di-, and/ or trialkyl-epsilon-caprolactone such as themonomethyl-, dimethyl-, trimethyl-, monoethyl-, diethyl-,triethylepsilon-caprolactones, and others exemplified supra; an alpha,alpha-dialkyl-beta-propiolactone and as alpha,alpha-dimethyl-beta-propiolactone; an alpha,alpha-dihaloalkyl-beta-propiolactone as illustrated by alpha, alphadichyoromethyl beta propiolactone; and others. Also highly preferredpolymeric diols include the socalled initiated lactone homopolyesterdiols which are prepared via the reaction of an admixture ofepsiloncaprolactone and an initiator which contains two groups from theclass of hydroxyl, primary amino, secondary amino, and mixtures thereof,in the presence of a catalyst such as stannous dioctanoate or stannictetraoctanoate.

Illustrative of the polyether glycols which are contemplated includethose illustrated previously as well as those illustrated in column 7,lines 19 through 70 of US. Pat. No. 2,929,804 which patent isincorporated by reference into this disclosure. Many of the polyesterdiols which are encompassed have been exemplified previously. Others areset forth in columns 4-5 of US. Pat. No. 3,097,192 which patent isincorporated by reference into this disclosure. The initiated lactonepolyester diols have been thoroughly illustrated previously; others aredisclosed in US. Pats. Nos. 2,878,236, 2,890,208, 2,914,556, and2,962,524 which patents are incorporated by reference into thisdisclosure. The polyurethane diols of Equation XI also represent apreferred group of substantially linear hydroxyl-terminated polymers.

The minimization or elimination of crystallinity, if present in thehydroxyl-terminated polymer, can be achieved, as oftentimes is desired,by introducing pendant groups and/or unsymmetrical groups in thepolymeric chain as illustrated by lower alkyl groups, e.g., methyl,ethyl, isopropyl, etc., halo, e.g., chloro, bromo, etc.; ortho-tolylene;and similar groups which do not interfere with the subsequentpolymerization under the conditions used. As is readily apparent tothose skilled in the art, the choice of the proper reactants willreadily yield hydroxyl-terminated polymers with the desired quantity andtype of pendant and/or unsymmetrical groups. Along this vein, polymersof desired molecular weight and melting point can thus be obtained. Inaddition, the polymer chain can be interrupted with divalent keto, urea,urethane, etc., groups.

The hydroxyl-terminated polymer and diisocyanate can be reacted in suchproportions so as to produce either a hydroxyl-terminated polyurethaneproduct or an isocyanato-terminated polyurethane product (prepolymer). Amolar ratio of diol to diisocyanate greater than one will yield thehydroxyl-terminated polyurethane whereas a molar ratio less than onewill result in the prepolymer.

As indicated previously, in a particularly useful embodiment, there isemployed a sufiicient molar excess of hydroxyl-terminated polymer, inparticular, the initiated lactone polyester diols, with relation to theorganic diisocyanate so that there results substantially linearhydroxyl-terminated polyurethane products which have average molecularweights of from about 1200 to about 5000, and preferably from about 1500to about 3800.

The hydroxyl-terminated polymers or the abovesaid hydroxyl-terminatedpolyurethane products then are linearly extended with the diisocyanatesof Formula I. This reaction can be carried out by employing a molarratio of diisocyanate to hydroxyl-terminated compound of from about1.1:1 to about 5:1 preferably from about 1.521 to about 3.5 :1, and morepreferably from about 2:1 to 2.5 :1.

In the preparation of the hydroxyl-terminated polyurethane products orthe prepolymer, the reaction temperature can vary over a broad rangesuch as noted for the isocyanato/active hydrogen (hydroxyl in thisinstance) section discussed previously. Of course, the optimum reactiontemperature will depend, to a significant degree, upon several variablessuch as the choice of reactants, the use of a catalyst, theconcentration of the reactants, etc. A suitable temperature range isfrom about 20 C. to about 125 C., and preferably from about 50 C. toabout C. The reaction time likewise is largely influenced by thecorrelation of the variables involved, and can vary from a few minutesto several hours, e.g., from about 0.5 to about 5 hours, and longer. Thetertiary amine compounds and/or the organic metal compounds disclosed inthe section which discusses the isocyanato/ active hydrogen reactionscan be employed as catalysts, if desired. The isocyanato/hydroxylreactions are suitably carried out in the absence of an inert normallyliquid organic vehicle, though one can be employed, if desired.

In the next step, the prepolymer which results from the above discussedisocyanato/hydroxyl reaction is reacted with a bifunctional curingcompound which possesses two groups that are reactive with isocyanatogroups. Examples of such curing compounds include diamines, diols, aminoalcohols, hydrazino compounds, e.g., hydrazine, water, and the like. Itis preferred that said curing compound have two reactive groups from theclass of alcoholic hydroxyl, primary amino, and second amino. The mostpreferred reactive group is primary amino. It is to be understood thatprimary amino (-NH and secondary amino (NHR) include those compounds inwhich the nitrogen of the these amino groups is bonded to a carbon atomas in, for example, ethylenediamine, as well as those compounds in whichsaid nitrogen (of these amino groups) is bonded to another nitrogen atomas in, for instance, hydrazine.

The bifunctional curing compounds have been illustrated previously inthe discussion of the active hydrogen compounds. Among the moredesirable diamines (which term includes the monoand polyalkylenepolyamines which have two and only two primary and/or secondary aminogroups) are such compounds as ethylenediamine, 1,2- and1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, the cyclohexylenediamines, the phenylenediamines,the tolylenediamines, 4,4-diaminodiphenylmethane, mand pxylylenediamine,3,3 dichloro 4,4 diaminophenylmethane, benzidine,1,5-diaminonaphthalene, piperazine, 1,4 bis(3 aminopropyl)piperazine,trans-2,5-dimethylpiperazine, and the like.

It is preferred that the diamine contain no groups other than the tworeactive amino groups that are reactive with isocyanato. The saiddiamine can have various substituent groups including chloro, bromo,alkoxy, alkyl, and the like. Generally it is also preferred that thediamine have not more than 15 carbon atoms.

Illustrative of the various diols and amino alcohols include thoseexemplified previously and, in particular, ethylene glycol, propyleneglycol, 2,2-dimethyl-1,3-propanediol, paradibenzyl alcohol,1,4-butanediol, ethanolarnine, isopropanolamine, and the like. Water andhydraz ne are also useful bifunctional curing agents. The organicd1amines are the preferred curing compounds, with the alkylenediaminesbeing more preferred, and ethylenediamine being most preferred.

The ratio of reactants in the curing step can vary from about 0.8 toabout 1.5 equivalents of isocyanato from the prepolymer per equivalentof functional group from the bifunctional curing compound. In manycases, it is desirable to employ approximate stoichiometric proportionsof prepolymer and curing compound, i.e., in proportions such that thereis present approximately one isocyanato group from the prepolymer perreactive group from the difunctional curing compound. Oftentimes, it isdesirable to employ a slight stoichiometric excess of prepolymer, e.g.,greater than about one equivalent and upwards to about 1.4 equivalentsof isocyanato per equivalent of functional group (from the bifunctionalcuring compound), and preferably from about 1.05 to about 1.2equivalents of isocyanato per equivalent of functional group.

A preferred method for carrying out the reaction of prepolymer withcuring compound is to effect the reaction in an inert normally liquidorganic solvent and thus form a solution from which the elastic fibersand films of the invention can be produced by conventional solutionspinning and casting techniques. This can be done by dissolving theprepolymer in a solvent to make, for example, from about to about 40weight percent solid solution (percent based on total solution weight),and then adding the bifunctional curing compound to this solution. Theaddition will be facilitated if the curing compound is also dissolved inthe same solvent. Many solvents can be used for this purpose. Theessential requirement is that the solvent be non-reactive with theprepolymer and with the curing compound. Examples of useful solventsinclude acetone, dimethyl sulfoxide, N,N-dimethylformamide,N,N-dimethylacetamide, tetrahydrofuran, and the like.N,N-dimethylformamide is a preferred solvent. Acetone alone or inadmixture with other organic vehicles such as those illustrated aboverepresent, by far, the most preferred solvents from commercial andeconomic standpoints. In this respect, it should be particularly notedthat commercial polyurethane fibers prepared from aromaticdiisocyanates, e.g., p,p'-methylenediphenyl diisocyanate (MDI), cannotbe spun or cast from an acetone system. In lieu thereof, the universalsolvent for the aforesaid commercial polyurethane fibers is theexpensive dimethylformamide.

The reaction between the prepolymer and the curing compound takes placereadily at room temperature. Therefore, the solution can be spun into afiber or cast into a film within a relatively short period, e.g., a fewminutes, after the curing compound has been added. For example, thesolution can usually be cast or spun within minutes after the additionof a diamine to the prepolymer when the reactants are at a temperatureof about 25 C. In making fibers, the polymer solution can be spun into awater bath, or dry spun, via conventional techniques. Liquids other thanwater can be employed in the bath, if desired, but water is generallypreferred for economic reasons. Ethylene glycol, glycerol, and the likeare illustrative of such other liquids. The temperature of the bath canbe varied over a range of, for instance, 25 C. to 150 C. The fiber isrecovered from the bath by conventional techniques, and can be given apost-cure to oftentimes enhance certain of the properties. A cure atelevated temperatures, for example, up to about 125 C., and higher, forperiods ranging from several minutes to several hours may be desirablein many instances. For the preparation of fibers, the cure can beconducted for a period, for example, as long as five hours whereas thecure can be increased to 16 hours, and longer, for the preparation offilms. In any event, the cure, if desired, can be varied in duration toobtain the desired and optimum properties in the final product.Conventional solution casting techniques can be employed in makingfilms.

If gelation should occur during the reaction between the prepolymer andthe curing compound in the solvent, it is oftentimes desirable to add asmall amount of acid to the prepolymer solution preferably before thecuring compound is added. By so doing, the storage life of the solutioncontaining the reaction product of prepolymer and curing compound can beincreased significantly, for example, from a storage life in some casesof only a few 38 minutes without the acid to a storage life of up toabout several days with the acid. The acid is used in small amounts. Forinstance, from about 0.005, and lower, weight percent to about 0.6weight percent of acid, and higher, based on the weight of theprepolymer, has been found to be suitable.

Laboratory tests have shown that the following acids and acid-formingcompounds are oftentimes useful for the purpose described in thepreceding paragraph: phosphoric acid, phosphorous acid, hydrochloricacid, nitric acid, sulfuric acid, benzoyl chloride, benzene sulfonylchloride, benzenesulfonic acid, dichloroacetic acid, octylphenyl acidphosphate, stearyl acid phosphate, and boron trifluoride-etherate. It isto be noted that the pK of each of the above mentioned acids is lessthan about 2.5. (The term pK refers to the negative of the log of thehydrogen ion ionization constant in aqueous solution.) The strongmineral acids which have a pK less than about 2.5 represent a preferredsubclass. Phosphoric acid is the preferred species.

The characteristics of the novel fibers and films can be varied over awide range depending, to a significant degree, on the choice andproportion of the hydroxyl terminated polymers (diol), the diiocyanatesource, and bifunctional curing compound, the reaction conditions, etc.The novel fibers and films can range from semi-elastic to highlyelastic. A uniqueness which should be stressed is the overallcombination of properties which oftentimes can be obtained such as wouldresult from fibers prepared via the reaction of lactone polyester diol,FDI, and piperazine. For instance, novel elastic fibers and films can beobtained by the practice of the invention which exhibit many of thefollowing characteristics.

The molecular weights of the resulting novel elastomeric fibers andfilms are somewhat difficult to ascertain with exactness. Nevertheless,they are sufficiently high enough so that significant semi-elastic andelastic properties in the filmand fiber-forming ranges result. Forinstance, novel elastic films and fibers (FDI, lactone polyester diol,and piperazine-diamine) can be obtained by the practice of the inventionwhich exhibit many of the following characteristics:

Tensile strength, p.s.i 8000 Elongation, percent 550 300% modulus, p.s.i1000 Stress decay, percent 31 Work recovery, percent 25 Tension set,percent 20 Stability in Fadeometer testNo discoloration after hoursexposure.

The novel elastic and semi-elastic polymers are highly usefulcompositions. For instance, in the form of fibers, the polymers can beused to make foundation garments, bathing suits, sporting clothes,elastic waist bands, hose, and the like. In the form of films, thepolymers can be employed as elastic sheeting, as rubber bands, and thelike.

Another highly significant aspect of the invention is the use of thenovel diisocyanates of Formula I, and/or the novel prepolymers, and/orthe novel polyisocyanato-containing polymers (especially the relativelylow molecular weight polymeric aliphatic multiisocyanates as illustratedby Units IXE and IXF supra), to prepare foams, e. g., polyurethanefoams, which can range from the extremely flexible to the highly rigidstate. The prepolymers which are contemplated in this aspect are thepolyisocyanato-containing reaction products which result from thereaction of polyfunctional compounds which contain two or more activehydrogen substituents as described previously, e.g., diols, triols,tetrols, diamines, triamines, amino alcohols, etc., with the noveldiisocyanates of Formula I. The proportions of the reactants are suchthat a sufficient stoichiometric excess of diisocyanates with relationto the polyfunctional compound is employed, i.e., the equivalents of

